JP2007163571A - Photosensitive resin composition for optical waveguide and optical waveguide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for an optical waveguide and so on, which have high heat resistance, of which the refractive index is easily heightened, and to which a difference in refractive indexes sufficient to fabricate an optical waveguide is imparted. <P>SOLUTION: The photosensitive resin composition for the optical waveguide contains a polymerizable compound (A) which has at least two or more alicyclic epoxy groups in the molecule and further which contains at least one or more aromatic rings in the molecule. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a photosensitive resin composition for an optical waveguide and an optical waveguide, and more specifically, various optical waveguides widely used in the fields of optical communication, optical information processing, micro devices, micro optics, and other general optics. The present invention relates to a photosensitive resin composition for an optical waveguide that can be used for an optical waveguide device, an optical integrated circuit or an optical printed wiring board, an optical / electrical composite printed wiring board, and an optical waveguide comprising the composition.
Also disclosed are a refractive index adjusting agent and a refractive index adjusting method for an optical waveguide obtained by curing an alicyclic epoxy polymerizable compound.

Used in various optical waveguides, optical waveguide devices, optical integrated circuits or optical printed wiring boards, optical / electrical composite printed wiring boards, etc. widely used in the fields of optical communication, optical information processing, micro devices, micro optics, and other general optics As an optical waveguide that can be formed, an optical waveguide using a polymer resin (photolithography) that can be formed by using an inexpensive material and a simple process has been studied.
On the other hand, the low cost of optical devices, which has been a problem in the past, due to the fact that the information transmission frequency is increasing and the limit of electric wiring is approaching, and the emergence of surface-emitting lasers (VCSEL), which are surface-mounted light emitting devices. And cost reduction of the entire system using the optical waveguide including mounting has been demanded (see Nikkei Electronics, December 3, 2001, P109-).
In the surface emitting laser (VCSEL) which is a surface mount type light emitting element, commercial production is proceeding for a light emitting wavelength of 850 nm. Since this surface emitting laser is different from 1300 nm or 1550 nm which is the wavelength of a semiconductor laser used in general long-distance optical communication, it is used separately from these long-distance communication systems. Most of them are used for communication within a device or device.
In such a case, the optical waveguide cross section becomes a multimode optical circuit corresponding to 40 to 100 μm square, and the optical circuit and the electric circuit, preferably a printed wiring board made of an organic material, are integrated for high-density mounting. A so-called optical / electric composite printed wiring board is desired. In such an application, a level of heat resistance required for a so-called printed wiring board is required for the resin forming the optical waveguide, and at the same time, the resin needs to have a small light propagation loss. At this time, it is essential to arbitrarily control the refractive index of the resin forming the optical waveguide to some extent.

Here, for example, in Patent Document 1, an optical resin having good heat resistance is obtained from an ultraviolet curable resin mainly composed of an alicyclic epoxy.
However, the refractive index of the cured product made of alicyclic epoxy as the main component is about 1.51. Assuming the case where this is used as a core layer of an optical waveguide, the cladding layer needs to have a lower refractive index, and it is necessary to introduce fluorine atoms or the like into the compound, leading to higher costs. In addition, the adhesion between the cladding layer and the substrate may be insufficient. Further, when a conventional fluorinated epoxy resin is used, there is a concern that the heat resistance is not good.
On the other hand, assuming the case where it is used as a cladding layer of an optical waveguide, it is necessary to add a bisphenol A epoxy resin or the like because the core layer needs to have a high refractive index, and there is a trade-off between heat resistance and high refractive index. There is a problem that arises. That is, in Patent Document 1, a heat-resistant optical resin that can be easily adjusted in refractive index suitable for producing an optical waveguide has not been obtained.

  Similarly, Patent Document 2 attempts to form a low-cost optical waveguide by a method of exposing and developing using a material blended with an alicyclic polyfunctional epoxy as a core material. However, since the cycloaliphatic polyfunctional epoxy has a low refractive index, if the refractive index of the optical waveguide is to be increased, the content of the cycloaliphatic polyfunctional epoxy has to be lowered. There is a problem in that there is a tradeoff with heat resistance resulting from use.

In Patent Document 3, a material in which an oligomer having an isocyanuric acid skeleton and a hydantoin skeleton is blended is used as a core / cladding material to achieve both high refractive index and heat resistance. However, when this oligomer is used, there is a concern that the core / cladding material has a very high viscosity and poor film thickness uniformity, resulting in a decrease in light propagation loss. Furthermore, since the reactive site of this oligomer is a glycidyl group, there is a problem that the reaction is difficult to complete unless heat treatment is performed after UV irradiation.
As described above, when forming a multimode optical waveguide by using a photosensitive polymer resin and photolithography, it is difficult to control the refractive index without sacrificing heat resistance and realizing high heat resistance, and light propagation loss. At present, an excellent optical waveguide has not been realized.

JP-A-6-228274 Patent registration No. 30603903 JP-A-2005-70558

  The present invention has been made in view of the above points, and has a high heat resistance, an easily increased refractive index, and an optical waveguide photosensitive material capable of providing a sufficient refractive index difference for producing an optical waveguide. An object of the present invention is to provide a conductive resin composition and an optical waveguide having both propagation loss and heat resistance.

As a result of intensive studies to solve the above-described problems of the prior art, the present inventors have found that the above problems can be solved by the following means.
(1) (A) A photosensitive resin composition for an optical waveguide containing a polymerizable compound having at least two or more alicyclic epoxy groups in the molecule and containing at least one or more aromatic rings in the molecule. object.
(2) The photosensitive resin composition for optical waveguides according to (1), wherein the polymerizable compound (A) is represented by the following general formula (1).
General formula (1)

（一般式（１）中、Ｅ¹¹およびＥ¹²は、それぞれ、脂環エポキシ基を表す。Ｒ¹¹およびＲ¹²は、それぞれ、単結合、２価の脂肪族炭化水素基、または２価の芳香族炭化水素基を表す。Ａ¹¹およびＡ¹²は、それぞれ、単結合、または−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−Ｏ−、−Ｓ−、−Ｎ（Ｒ¹³）−（Ｒ¹³は水素原子または炭素数１〜２０のアルキル基を表す）、およびこれらの組み合わせからなる基を表す。Ａｒ¹¹は、２価の芳香族炭化水素基を表す。ａおよびｃは、それぞれ、１〜３の整数を表す。ｂは、０〜３の整数を表す。ｂ＝０の場合、Ｅ¹¹およびＥ¹²の少なくとも片方は、芳香環を含有する置換基を有した脂環エポキシ基を表す。）
（３）さらに、（Ｂ）光酸発生剤を含有する、（１）または（２）に記載の光導波路用感光性樹脂組成物。
（４）コア層とクラッド層とを有し、前記コア層が、（１）〜（３）のいずれか１項に記載の光導波路用感光性樹脂組成物の硬化物からなる、光導波路。
（５）コア層とクラッド層とを有し、前記コア層と前記クラッド層のいずれも、重合性化合物として脂環エポキシ化合物のみを含む光導波路用感光性樹脂組成物の硬化物からなる、光導波路。
（６）前記コア層は、（１）〜（３）のいずれか１項に記載の光導波路用感光性樹脂組成物の硬化物からなる、（５）に記載の光導波路。
（７）脂環エポキシ重合性化合物を硬化してなる光導波路の屈折率調整剤であって、（Ａ）分子内に少なくとも２つ以上の脂環エポキシ基を有し、かつ、分子内に少なくとも１つ以上の芳香環を含有する重合性化合物を含む、屈折率調整剤。
（８）脂環エポキシ重合性化合物を硬化してなる光導波路の屈折率調整方法であって、（Ａ）分子内に少なくとも２つ以上の脂環エポキシ基を有し、かつ、分子内に少なくとも１つ以上の芳香環を含有する重合性化合物を用いることを含む、屈折率調整方法。

(In the general formula (1), E ¹¹ and E ¹² each represent an alicyclic epoxy group. R ¹¹ and R ¹² each represent a single bond, a divalent aliphatic hydrocarbon group, or a divalent aroma. A ¹¹ and A ¹² each represent a single bond, or —SO—, —SO ₂ —, —CO—, —O—, —S—, —N (R ¹³ ) — (R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), and a group composed of a combination thereof, Ar ¹¹ represents a divalent aromatic hydrocarbon group, and a and c are each 1 Represents an integer of ˜3, b represents an integer of 0 to 3. When b = 0, at least one of E ¹¹ and E ¹² represents an alicyclic epoxy group having a substituent containing an aromatic ring. .)
(3) The photosensitive resin composition for an optical waveguide according to (1) or (2), further comprising (B) a photoacid generator.
(4) An optical waveguide comprising a core layer and a clad layer, wherein the core layer is made of a cured product of the photosensitive resin composition for an optical waveguide according to any one of (1) to (3).
(5) An optical waveguide comprising a cured product of a photosensitive resin composition for an optical waveguide that includes a core layer and a cladding layer, and each of the core layer and the cladding layer includes only an alicyclic epoxy compound as a polymerizable compound. Waveguide.
(6) The optical waveguide according to (5), wherein the core layer is made of a cured product of the photosensitive resin composition for optical waveguides according to any one of (1) to (3).
(7) A refractive index adjuster for an optical waveguide obtained by curing an alicyclic epoxy polymerizable compound, (A) having at least two alicyclic epoxy groups in the molecule, and at least in the molecule A refractive index adjusting agent comprising a polymerizable compound containing one or more aromatic rings.
(8) A method for adjusting the refractive index of an optical waveguide obtained by curing an alicyclic epoxy polymerizable compound, (A) having at least two alicyclic epoxy groups in the molecule, and at least in the molecule A method for adjusting a refractive index, comprising using a polymerizable compound containing one or more aromatic rings.

  The photosensitive resin composition for an optical waveguide of the present invention has good solder heat resistance, and can also provide a refractive index difference sufficient for use as a core layer and a cladding layer in the production of an optical waveguide. . Moreover, it has become possible to increase the refractive index as compared with a composition using a conventional alicyclic epoxy. As a result, it is possible to obtain both a photosensitive resin composition for a high heat resistant core layer and a high heat resistant clad layer, and it is possible to achieve both propagation loss and heat resistance when used as an optical waveguide. is there. In particular, the present invention is extremely advantageous in that both heat resistance and high refractive index can be achieved.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

Photosensitive resin composition for optical waveguide The photosensitive resin composition for an optical waveguide of the present invention has (A) at least two or more alicyclic epoxy groups in the molecule, and at least one or more in the molecule. It contains a polymerizable compound containing an aromatic ring (hereinafter sometimes referred to as “(A) polymerizable compound”). More preferably, it further contains (B) a photoacid generator.

1. (A) Polymerizable compound (A) The polymerizable compound is a polymerizable compound having at least two alicyclic epoxy groups in the molecule and containing at least one aromatic ring in the molecule. It is preferably cationically polymerizable.
The alicyclic epoxy group in the present invention refers to a structure obtained by epoxidizing alicyclic olefins. Specifically, the following (E-1) to (E-7) are preferable examples.

（Ｅ−１）〜（Ｅ−７）中、ここで、Ｒは芳香環を含有していてもよい１価の有機基を表す。ｎは０〜３の整数を表す。Ｒは、重合性化合物の他の部分と結合して環構造を形成していてもよい。またＲは、互いに結合していてもよい。重合性化合物の他の部分と結合して環構造を形成する場合とは、例えば、後で例示する一般式（１）の例示化合物Ａ−２８、Ａ−２９等のような場合である。また、ｎが２以上の場合、Ｒは、それぞれ、同一であっても異なっていてもよい。

In (E-1) to (E-7), R represents a monovalent organic group which may contain an aromatic ring. n represents an integer of 0 to 3. R may combine with other moieties of the polymerizable compound to form a ring structure. R may be bonded to each other. The case of forming a ring structure by combining with the other part of the polymerizable compound is, for example, the case of exemplified compounds A-28, A-29, etc. of the general formula (1) exemplified later. When n is 2 or more, Rs may be the same or different.

(A) The polymerizable compound preferably has a structure represented by the following general formula (1).
General formula (1)

In the general formula (1), E ¹¹ and E ¹² each represent an alicyclic epoxy group. The alicyclic epoxy group may have a substituent. The substituent is not particularly defined, and examples thereof include an aromatic ring or a group containing the aromatic ring.
E ¹¹ and E ¹² are each preferably any one of examples E-1 to E-7 of the alicyclic epoxy group, more preferably any of E-1 to E-3, -2 or E-3 is more preferable, and E-2 is most preferable.

R ¹¹ and R ¹² each represents a single bond, a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group. The divalent aliphatic hydrocarbon group or the divalent aromatic hydrocarbon group may have a substituent. The substituent is not particularly defined, but is preferably an alkoxy group or a halogen atom.
R ¹¹ and R ¹² are each preferably a single bond, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, or an aralkylene group having 7 to 15 carbon atoms. An alkylene group is more preferable, and a single bond or an alkylene group having 1 to 8 carbon atoms is most preferable.

A ¹¹ and A ¹² are each a single bond, or —SO—, —SO ₂ —, —CO—, —O—, —S—, —N (R ¹³ ) — (R ¹³ is a hydrogen atom or a carbon number; 1 to 20 alkyl groups), and a group composed of a combination thereof. Here, the aforementioned "group consisting of the combination", for example, -OCO -, - COO -, - N (R 13) CO -, - CON (R 13) -, - N (R 13) COO- ^{, -N (R 13) CON (} R 13) -, - SO 2 N (R 13) -, - COS- like.
R ¹³ may combine with a substituent of the epoxy group of E ¹¹ and E ¹² to form a ring.
A ¹¹ and A ¹² are each a single bond, —SO—, —SO ₂ —, —CO—, —O—, —S—, —OCO—, —COO—, —N (R ¹³ ) CO—, —CON (R ¹³ ) — and —N (R ¹³ ) COO— (wherein R ¹³ represents an alkyl group having 1 to 20 carbon atoms) are preferable, and a single bond, —CO—, —O—, — S -, - OCO -, - COO -, - N (R 13) CO -, - CON (R 13) - is more preferably a single bond, -O -, - OCO -, - COO- are particularly preferred.

Ar ¹¹ represents a divalent aromatic hydrocarbon group. The divalent aromatic hydrocarbon group may have a substituent. Examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogen atom.
Ar ¹¹ is preferably an arylene group having 6 to 50 carbon atoms or an aralkylene group having 7 to 50 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms or an aralkylene group having 7 to 20 carbon atoms. A 6-15 arylene group or a C7-15 aralkylene group is more preferable.

a and c each represent an integer of 1 to 3; b represents an integer of 0 to 3. When b = 0, at least one of E ¹¹ and E ¹² represents an alicyclic epoxy group having a substituent containing an aromatic ring.
When a, b and c are 2 or more, that is, when two or more of R ¹¹ , A ¹¹ , Ar ¹¹ , A ¹² and R ¹² are present, R ¹¹ , A ¹¹ , Ar ¹¹ , A ¹² , R ¹² may be the same or different.

  Preferable specific examples of the polymerizable compound represented by the general formula (1) include the following compounds.

These (A) polymerizable compounds may be used alone or in combination of two or more. Even if the photosensitive resin composition for optical waveguides of the present invention contains only the polymerizable compound (A) as a polymerizable compound, a polymerizable compound other than the polymerizable compound (A) is mixed and used. Also good.
The polymerizable compound contained in the photosensitive resin composition for an optical waveguide of the present invention is a compound containing only the polymerizable compound (A) or a compound mixed with an alicyclic epoxy compound having no aromatic ring. The use of an epoxy compound alone is preferable in that an optical waveguide having extremely excellent heat resistance can be obtained.
Examples of the alicyclic epoxy compound having no aromatic ring include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylethyl-8,4-epoxycyclohexanecarboxylate, vinylcyclohexene. Dioxide, allyl cyclohexylene dioxide, 8,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m -Dioxane, bis (3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bi (3,4-epoxycyclohexyl) diethylsiloxane, Epolide GT-301 (epoxy equivalent 200-220, manufactured by Daicel Chemical Industries, Ltd.), Epolide GT-401 (epoxy equivalent 210-235, manufactured by Daicel Chemical Industries, Ltd.) Etc.

  Moreover, you may mix and use polymeric compounds other than the said (A) polymeric compound for the photosensitive resin composition for optical waveguides of this invention. Examples of such compounds include other epoxy compounds, oxetane compounds, and vinyl compounds.

  Other epoxy compounds include polybutadiene diglycidyl ether, poly-1,4- (2,3-epoxybutane) -CO-1,2- (8,4-epoxy) -CO-1,4-butadiene diol, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, O-phthalic acid glycidyl ester, trimethylolpropane polyglycidyl ether , Diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, Nyl glycidyl ether, phenol penta (oxyethylene) glycidyl ether, p-tert-butylphenyl glycidyl ether, dibromophenyl glycidyl ether, lauryl alcohol pentadeca (oxyethylene) glycidyl ether, sorbitan polyglycidyl ether, pentaerythritol 4 tol polyglycidyl ether, Triglycidyl tris (2-hydroxyethyl) isocyanurate, resorcin diglycidyl ether, polytetramethylene glycol diglycidyl ether, adipic acid diglycidyl ester, hydroquinone diglycidyl ether, bisphenol S diglycidyl ether, terephthalic acid diglycidyl ester, glycidyl phthalimide , Dibromophenyl glycidyl ether, dibromoneope Tyl glycol diglycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, p-octylphenyl glycidyl ether, p-phenylphenyl glycidyl ether, glycidyl benzoate, glycidyl acetate, glycidyl butyrate, spiroglycol diglycidyl ether, reduced maltose polyglycidyl ether, Bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol G diglycidyl ether, bisphenol G diglycidyl ether, tetramethylbisphenol A diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, bisphenol C diglycidyl ether, 1, 3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoroethyl) benzene, 1,4-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoroethyl ) Benzene, 4,4'-bis (2,3-epoxypropoxy) octafluorobiphenyl, tetraglycidyl-m-xylylenediamine, tetraglycidyldiaminodiphenylmethane, triglycidyl-paraaminophenol, triglycidyl-metaaminophenol, diglycidyl Aniline, diglycidyl tribromoaniline, tetraglycidyl bisaminomethylcyclohexane, tetrafluoropropyl glycidyl ether, octafluoropentyl glycidyl ether, dodecafluorooctyl diglycidyl ether, styrene oxide, limonate Diepoxide, limonene monoxide, alpha-pinene epoxide, such as β- pinene epoxide and the like. It is also possible to use a fluorinated epoxy compound described in JP-A No. 2004-117955.

  As the oxetane compound, 3-ethyl-3-hydroxymethyloxetane (trade name “OXT-101”, manufactured by Toagosei Co., Ltd.), 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl } Benzene (trade name “OXT-121”, manufactured by Toa Gosei Co., Ltd.), 3-ethyl-3-phenoxymethyloxetane (trade name “OXT-211”, manufactured by Toa Gosei Co., Ltd.), bis (3-ethyl) -3-oxetanylmethyl) ether (trade name “OXT-221”, manufactured by Toa Gosei Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (trade name “OXT-212”, Toa Gosei) Oxetane resin (trade name “OX-SQ”, Toa Gosei Co., Ltd.) with γ- (3-ethyl-3-oxetanylmethoxy) propyl group attached to the silsesquioxane skeleton. ) Ltd.), 3-ethyl-3-oxetanyl methanol and phenol ether novolak structure oxetane resin (trade name "PNOX", and the like can be exemplified by Toagosei Co., Ltd.).

  Examples of the vinyl compound include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, vinyl ethers such as 1,4-cyclohexanedimethanol divinyl ether, and styrenes such as methylstyrene, methoxystyrene, and divinylbenzene. It is done.

  The content of the polymerizable compound (A) is not particularly limited, and is appropriately determined in consideration of the requirements for the viscosity, refractive index, curability, and cured product performance of the photosensitive resin composition for an optical waveguide. It is done. Specifically, the content of the polymerizable compound (A) is preferably 5 to 90% by mass and more preferably 10 to 85% by mass with respect to the weight of the total polymerizable compound in the photosensitive resin composition for an optical waveguide. 15 to 80% by mass is preferable.

2. (B) Photoacid generator As a method for causing the curing action of the photosensitive resin composition for an optical waveguide containing the polymerizable compound (A), a method using a photoacid generator or a method using a thermal acid generator can be mentioned. . A method using a photoacid generator is preferred. Hereinafter, the photoacid generator that can be used in the present invention will be described in detail.

Here, the photoacid generator refers to a compound that releases an acidic active substance (Lewis acid) that causes a photocuring action of the photosensitive resin composition for an optical waveguide containing the polymerizable compound (A) by irradiation of radiation. . Examples of radiation include visible light, ultraviolet rays, infrared rays, X-rays, electron beams, α rays, γ rays, etc., but from a viewpoint of having a certain energy level and being relatively inexpensive and small in size. It is preferable to use ultraviolet rays.
Examples of the photoacid generator include onium salts, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, and disulfonylmethane compounds.

<Onium salt>
Examples of onium salts include sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts, ferrocene, and the like.

  Examples of the photoacid generator of the sulfonium salt include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, and bis [4- ( Diphenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (diphenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) pheny Sulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis {4- [di [4 -(2-hydroxyethoxy)] phenylsulfonio] phenyl} sulfide bishexafluorophosphate, bis {4- [di [4- (2-hydroxyethoxy)] phenylsulfonio] phenyl} sulfide bishexafluoroantimonate, bis {4- [di [4- (2-hydroxyethoxy)] phenylsulfonio] phenyl} sulfide bistetrafluoroborate, bis {4- [di [4- (2 Hydroxyethoxy) phenylsulfonio] phenyl} sulfide tetrakis (pentafluorophenyl) borate, and the like.

  Photoacid generators for iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (Dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexa Fluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyl Nyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate, etc. Can be mentioned.

  Phosphonium salt photoacid generators include ethyltriphenylphosphonium tetrafluoroborate, ethyltriphenylphosphonium hexafluorophosphate, ethyltriphenylphosphonium hexafluoroantimonate, tetrabutylphosphonium tetrafluoroborate, tetrabutylphosphonium hexafluorophosphate, tetra Examples thereof include butylphosphonium hexafluoroantimonate.

  Examples of the photoacid generator of the diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrakis (pentafluorophenyl) borate and the like.

  As photoacid generators of ammonium salts, 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl 2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) Examples include 2-cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.

  Examples of photoacid generators for pyridinium salts include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl 2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) Examples include 2-cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.

  Ferrocene photoacid generators include (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) hexafluorophosphate, (2,4-cyclopentadien-1-yl). ) [(1-methylethyl) benzene] -Fe (II) hexafluoroantimonate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) tetrafluoroborate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) tetrakis (pentafluorophenyl) borate, and the like.

<Sulfone compound>
Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof. Specific examples of the sulfone compound include phenacylphenylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, 4-trisphenacylsulfone, and the like.

<Sulfonate compound>
Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
Specific examples of the sulfonate compound include benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, pyrogallol trisnonafluorobutanesulfonate, pyrogallolmethanesulfonic acid triester, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, α -Methylol benzoin tosylate, α-methylol benzoin octane sulfonate, α-methylol benzoin trifluoromethane sulfonate, α-methylol benzoindodecyl sulfonate, and the like.

<Sulfonimide compound>
Examples of the sulfonimide compound include compounds represented by the following general formula (9).

General formula (9)

一般式（９）中、Ｒ²は、２価の基を表し、アルキレン基またはアリーレン基が好ましい。Ｒ³は、１価の基を表し、アルキル基またはアリール基を表す。これらの基は、置換基（例えば、ハロゲン原子）で置換されていてもよい。

In general formula (9), R ² represents a divalent group, and is preferably an alkylene group or an arylene group. R ³ represents a monovalent group and represents an alkyl group or an aryl group. These groups may be substituted with a substituent (for example, a halogen atom).

  Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (p-toluenesulfonyl). Oxy) diphenylmaleimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (perfluorooctanesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3- Dicarboximide, N- (perfluorooctanesulfonyloxy) naphthylimide, N- ( Benzenesulfonyloxy) succinimide, N- (benzenesulfonyloxy) phthalimide, N- (benzenesulfonyloxy) diphenylmaleimide, N- (benzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide, N- (benzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (benzenesulfonyloxy) bicyclo [2.2. 1] Heptane-5,6-oxy-2,3-dicarboximide, N- (benzenesulfonyloxy) naphthylimide and the like.

<Disulfonyldiazomethane compound>
Examples of the disulfonyldiazomethane compound include compounds represented by the following general formula (10).

General formula (10)

一般式（１０）中、Ｒ⁴およびＲ⁵は、それぞれ、１価の基を表し、アルキル基またはアリール基が好ましい。これらの基は、置換基（例えば、ハロゲン原子）で置換されていてもよい。

In the general formula (10), R ⁴ and R ⁵ each represent a monovalent group, preferably an alkyl group or an aryl group. These groups may be substituted with a substituent (for example, a halogen atom).

  Specific examples of the disulfonyldiazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and bis (2,4-dimethylbenzene). Sulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, bis (p-tert-butylphenylsulfonyl) diazomethane, bis (p-chlorobenzenesulfonyl) diazomethane, cyclohexylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (1-methylethyl) Sulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5,5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4,5] decan-7-sulfonyl) diazomethane, etc. Can be mentioned.

<Disulfonylmethane compound>
Examples of the disulfonylmethane compound include a compound represented by the following formula (11).

式（１１）中、Ｒ⁶およびＲ⁷は、それぞれ、有機基を表し、１価の直鎖状若しくは分岐状の脂肪族炭化水素基、シクロアルキル基、アリール基、アラルキル基またはヘテロ原子を有する有機基であることが好ましい。
ＶおよびＷは、それぞれ、有機基を表し、アリール基、水素原子、１価の直鎖状若しくは分岐状の脂肪族炭化水素基またはヘテロ原子を有する有機基であることが好ましい。但し、ＶおよびＷの少なくとも一方がアリール基であるか、ＶとＷが相互に連結して少なくとも１個の不飽和結合を有する単環または多環を形成しているか、ＶとＷが相互に連結して式（１２）で表される基を形成している。

In formula (11), R ⁶ and R ⁷ each represents an organic group, and each has a monovalent linear or branched aliphatic hydrocarbon group, cycloalkyl group, aryl group, aralkyl group, or heteroatom. An organic group is preferred.
V and W each represents an organic group, and are preferably an aryl group, a hydrogen atom, a monovalent linear or branched aliphatic hydrocarbon group, or an organic group having a hetero atom. However, at least one of V and W is an aryl group, or V and W are connected to each other to form a monocyclic or polycyclic ring having at least one unsaturated bond, or V and W are mutually They are linked to form a group represented by the formula (12).

式（１２）中、Ｖ’およびＷ’は、それぞれ、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アリール基またはアラルキル基を示すか、同一若しくは異なる炭素原子に結合したＶ’とＷ’が相互に連結して炭素単環構造を形成する。複数存在するＶ’およびＷ’はそれぞれ同一でも異なってもよい。ｎ１２は２〜１０の整数である。

In the formula (12), V ′ and W ′ each represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, or V ′ and W ′ bonded to the same or different carbon atoms. Are linked together to form a carbon monocyclic structure. A plurality of V ′ and W ′ may be the same or different. n12 is an integer of 2-10.

Of these photoacid generators, onium salts are preferable from the viewpoint of curing speed, stability, and economy, and among them, sulfonium salts and iodonium salts are more preferable.
As these commercial products, SP-150, SP-170, CP-66, CP-77 manufactured by Asahi Denka Kogyo Co., Ltd .; CYRACURE-UVI-6990, UVI-6974 manufactured by Union Carbide Co., Ltd .; Nippon Soda Co., Ltd. CI-2855, CI-2639 manufactured by Sanshin Chemical Industry Co., Ltd. Sun-Aid SI-60; Irgacure 261 manufactured by Ciba Specialty Chemicals Co., Ltd. (2,4-cyclopentadien-1-yl) [(1 -Methylethyl) benzene] -Fe (II) hexafluorophosphate); Rhodosil 2074, [4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl), manufactured by Rhone Pulan ) Borate] and the like.

  (B) A photo-acid generator can be used alone or in combination of two or more. (B) The usage-amount of a photo-acid generator does not have a restriction | limiting in particular, It is 0.05-25 mass% normally based on the weight of all the (A) polymeric compounds in the photosensitive resin composition for optical waveguides. From the viewpoint of curability and performance of the cured product, the content is preferably 1 to 20% by mass.

3. Other Components In the photosensitive resin composition for an optical waveguide of the present invention, a silane coupling agent may be used for improving the adhesiveness at the interface between the cured product and the circuit board.
Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N -Bis [β- (aminoethyl)]-γ-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyl Trimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, Hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyl Dichlorosilane, trimethylchlorosilane, vinyltriethoxysilane, benzyltrimethylsilane, vinyltris (2-methoxyethoxy) silane, γ-methacryloxypropyltris (2-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltri Examples include methoxysilane, γ-ureidopropyltriethoxysilane, γ-isocyanurylpropyltriethoxysilane, and n-octyltriethoxysilane.

Moreover, you may use a sensitizer for the photosensitive resin composition for optical waveguides of this invention in order to improve a sensitivity.
Examples of the sensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and isoamyl 4-dimethylaminobenzoate. Such as tertiary amines such as xanthene, thioxanthene, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-dichlorothioxanthone, coumarin, thiocoumarin, pyrene, perylene, phenothiazine, etc. Can be mentioned.

  Furthermore, a flame retardant, a low elasticity agent, a diluent, an antifoamer, an ion trap agent, a sea surface active agent, etc. can be mix | blended as needed.

4). Optical Waveguide 4-1 Structure of Optical Waveguide The optical waveguide of the present invention has a core layer and a clad layer, and preferably a base material, a lower clad layer formed on the base material, and an upper surface of the lower clad layer A core layer formed on a part of the upper clad layer, and an upper clad layer formed on the lower clad layer so as to embed the core layer. Here, at least the core layer is preferably made of a cured product of the photosensitive resin composition for an optical waveguide of the present invention.
The materials and shapes of the lower cladding layer, the core layer, and the upper cladding layer are selected in consideration of the relationship between the refractive indexes of these cured products satisfying the conditions required for the optical waveguide. For example, the width and height of the core layer is 5 to 100 μm, and the difference in refractive index between the core layer and the cladding layer is 0.2 to 10%, more preferably 1.0 to 5.0%. You can choose to be.

  The adjustment of the refractive index can be performed, for example, by appropriately selecting the type of substituents of the constituent raw materials of the photosensitive resin composition. Specifically, after selecting two or three types of photosensitive resin compositions that have an appropriate difference in refractive index, the composition having the highest refractive index is used as the material for the core layer, The composition may be used as a material for the cladding layers (lower cladding layer and upper cladding layer). Note that it is preferable to use the same material for the lower clad layer and the upper clad layer because it is economically advantageous and manufacturing management is easy.

  Moreover, when preparing the photosensitive resin composition for optical waveguides, the viscosity of the composition is preferably set to a value in the range of 100 to 10,000 mPa · s (25 ° C.), and is preferably 100 to 8,000 mPa · s. It is more preferable to set it as the value within the range of s (25 degreeC), and it is further more preferable to set it as the value within the range of 300-3,000 mPa * s (25 degreeC). When the viscosity is out of the above range, it may be difficult to handle the photosensitive resin composition or to form a coating film having a uniform thickness. The viscosity of the photosensitive resin composition can be adjusted by adding an appropriate amount of a reactive diluent or an organic solvent, but from the viewpoint of the properties of the cured product, no organic solvent is used. A solvent-free composition is preferred.

4-2 Method for Manufacturing Optical Waveguide As a method for manufacturing an optical waveguide, for example, a direct exposure method (Japanese Patent Laid-Open No. 2001-4858), a photobleaching method (Japanese Patent Laid-Open No. 2002-311262), and the like. And a molding method (Japanese Patent Laid-Open No. 2003-172841, etc.).
An example of a method for producing an optical waveguide by a wet lithography method using the photosensitive resin composition of the present invention will be described using an example of a so-called channel type optical waveguide. FIG. 1 is a flowchart showing an example of a method for producing an optical waveguide using the photosensitive resin composition of the present invention.
First, as shown to (a) in FIG. 1, the board | substrate 1 which has a flat upper surface as a base material is prepared. Examples of the substrate 1 include a silicon substrate, a glass substrate, and a polyimide substrate. Next, as shown in FIG. 1 (b), a photosensitive resin composition 2 for the lower cladding layer is applied to the upper surface of the substrate 1, and as shown in FIG. To form a lower clad layer 4. It is cured.

  Here, the photosensitive resin composition for the lower clad layer may be the photosensitive resin composition for an optical waveguide of the present invention, or other photosensitive resin composition. Preferably, the photosensitive resin composition for optical waveguides which a polymeric compound consists only of an alicyclic epoxy compound is employ | adopted. Since the polymerizable compound represented by the general formula (1) also serves as a refractive index adjusting agent (particularly a refractive index increasing agent) of the photosensitive resin composition for optical waveguides, both the clad layer and the core layer are used. It is also possible to employ the photosensitive resin composition for an optical waveguide of the present invention.

  Here, the coating method of the resin composition 2 is not particularly limited as long as the thickness of the lower clad layer (cured film) 4 is uniform and the surface becomes smooth. For example, a spin coating method, a spray method, a roll Methods such as a coating method and an inkjet method can be employed. Among these, the spin coating method used as a highly accurate industrial coating technique in the semiconductor industry is preferable. The spin coating method includes a first step of uniformly applying a liquid composition, which is performed under conditions of 1 to 60 seconds at a speed of 10 to 1,000 rpm at a temperature of 0 to 100 ° C., And a second step of forming a constant film thickness by high-speed rotation. Among these, in the second step, the surface roughness of the cured film is mainly controlled. In the second step, the conditions for the spin coating method are determined according to the viscosity of the liquid composition. For example, when the viscosity of the liquid composition is 100 to 3,000 mPa · s, the rotation is performed at 500 to 5,000 rpm for 30 to 100 seconds, and the viscosity is 3,000 to 10,000 mPa · s. Rotation for 60 to 300 seconds is performed at 1,000 to 8,000 rotations / minute. In addition, it can consider similarly to application | coating of the resin composition 2 also about the coating method of the resin compositions 5 and 8 mentioned later.

Moreover, visible light, ultraviolet rays, infrared rays, X-rays, electron beams, α rays, γ rays and the like can be used as the light 3 to be irradiated, and although not particularly limited, the industrial versatility of the light source In view of the above, light in the ultraviolet to visible region of 200 to 450 nm, preferably light containing ultraviolet light having a wavelength of 365 nm is usually used. As an example of irradiation conditions, exposure is performed by irradiating light with a wavelength of 200 to 450 nm so that the illuminance is 1 to 1000 mW / cm ² and the irradiation amount is 0.01 to 50 J / cm ^2. .
Examples of the light irradiation device include a lamp light source that simultaneously irradiates a wide area such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and an excimer lamp, a light source such as a pulsed or continuous light source, a mirror, a lens, An apparatus configured to obtain convergent light using an optical fiber is used. In the case of forming an optical waveguide using such convergent light, exposure can be performed so that the shape of the optical waveguide can be obtained by moving the convergent light or the irradiated object. Among the light sources used in the light irradiation device, a light source having a high ultraviolet intensity of 365 nm is preferable. For example, a high pressure mercury lamp is preferable as the lamp light source, and an argon laser is preferable as the laser light source.
When the liquid composition such as the resin composition 2 is cured by light irradiation, it is preferable that the entire thin film of the liquid composition is irradiated with light to cure the entire thin film.
The method of irradiating the resin compositions 5 and 8 described later with light 3 such as ultraviolet rays is the same as that of the resin composition 2.
Of course, it may be cured by other methods.

  Next, as shown in FIG. 1 (d), the photosensitive resin composition 5 for optical waveguide of the present invention for forming a core layer on the upper surface of the lower cladding layer 4 (having a refractive index higher than that of the cladding layer). After applying the photosensitive resin composition), as shown in FIG. 1 (e), the light is irradiated through the photomask 6 having a predetermined line pattern and exposed to form a core layer. The photosensitive resin composition 5 for an optical waveguide of the invention is cured.

In addition, as a method of performing light irradiation according to a predetermined pattern, it is not restricted to the method of using the photomask 6 which consists of a light transmission part and a non-transmission part, For example, the method of ac shown below is employ | adopted. Also good.
a. A method using electro-optically forming a mask image composed of a light transmission region and a non-transmission region according to a predetermined pattern, using the same principle as that of a liquid crystal display device.
b. A method of irradiating light through an optical fiber corresponding to a predetermined pattern in the light guide member using a light guide member formed by bundling a large number of optical fibers.
c. A method of irradiating a composition while scanning convergent light obtained by a condensing optical system such as a laser beam, a lens or a mirror.

  Next, as shown in FIG. 1 (f), by utilizing the difference in solubility between the cured part and the uncured part, the unexposed part is removed with a developer, and the core part 7 consisting only of the exposed part is removed. Form. Thereafter, drying or pre-baking may be performed as necessary, and irradiation with light 3 may be performed, or heat treatment (post-bake treatment) may be performed in order to promote curing of the exposed portion.

Here, as the developer, for example, an organic solvent such as methyl ethyl ketone, acetone, toluene, tetrahydrofuran, alcohol or the like is used. The development time is usually 30 to 600 seconds. As a developing method, a known method such as a liquid piling method, a dipping method, or a shower developing method can be employed. When a developer containing an organic solvent such as acetone is used as a developing solution, a patterned film (core layer 7) is formed by air drying as it is.
Next, as shown in (g) of FIG. 1, a photosensitive resin composition 8 for the upper cladding layer is applied, and as shown in (h) of FIG. Then, the upper clad layer 9 is formed. The upper cladding layer 9 may be further post-baked in order to improve hardness and heat resistance.
Thus, the optical waveguide 10 shown in (i) of FIG. 1 is completed. In the present specification, the term “optical waveguide” refers to having a clad layer and a core layer, and in principle, means a laminate composed of a clad layer and a core layer not including the substrate 1. The substrate 1 may be referred to as an optical waveguide.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Synthesis Example 1>
When a mixed solution (two-layer system) of 70 parts by mass of potassium hydroxide, 70 parts by mass of distilled water, 40 parts by mass of toluene and 3.1 parts by mass of tetrabutylammonium bromide is stirred in an ice bath, A solution consisting of 22.3 parts by mass of sen-1-methanol, 23.8 parts by mass of m-xylylene dibromide and 100 parts by mass of toluene was separately added dropwise over 30 minutes. After completion of the dropwise addition, the reaction was allowed to stir at room temperature for an additional 5 hours. The reaction solution was allowed to stand, the organic layer was taken out, washed with saturated brine, and the organic layer was concentrated. The obtained oily product was purified by column chromatography to obtain 19.3 parts by mass of an alicyclic olefin compound having the following structure.

Subsequently, 19.3 parts by mass of the alicyclic olefin compound and 250 parts by mass of chloroform are stirred in an ice bath, and 32.1 parts by mass of m-chloroperbenzoic acid is divided into three portions. did. After the addition, the reaction was continued at room temperature with stirring for another 5 hours. ¹ H NMR confirmed that the proton signal derived from the alicyclic olefin had completely disappeared. The obtained reaction solution was washed with an aqueous sodium thiosulfate solution, an aqueous sodium hydrogen carbonate solution, and saturated brine, and then the organic layer was concentrated to obtain 20.6 parts by mass of the following oily polymerizable compound (A-11).

<Synthesis Example 2>
22.8 parts by mass of cis-1,2-cyclohexene dicarboxylic acid anhydride and 22.8 parts by mass of methanol were reacted at 50 ° C. for 20 hours with stirring. The reaction solution was concentrated and dried to obtain 27.3 parts by mass of a white solid compound (2-1).

Compound (2-1)

３−シクロヘキセン−１−メタノール２２．４質量部、ジメチルアセトアミド（ＤＭＡｃ）１００質量部を氷浴下で攪拌しているところに、ｐ−クロロメチル安息香酸クロリド４５．４質量部とＤＭＡｃ１００質量部の混合溶液を滴下した。滴下終了後、室温でさらに５時間攪拌しながら反応させた。反応液に酢酸エチルを２００質量部加え、炭酸水素ナトリウム水溶液、蒸留水、飽和食塩水で洗浄後、有機層を濃縮した。得られたオイル状生成物をカラムクロマトグラフィーで精製することにより、下記構造の脂環オレフィン化合物（２−２）３３．４質量部を得た。

While stirring 22.4 parts by mass of 3-cyclohexene-1-methanol and 100 parts by mass of dimethylacetamide (DMAc) in an ice bath, 45.4 parts by mass of p-chloromethylbenzoic acid chloride and 100 parts by mass of DMAc were added. The mixed solution was added dropwise. After completion of the dropwise addition, the reaction was allowed to stir at room temperature for an additional 5 hours. To the reaction solution, 200 parts by mass of ethyl acetate was added, and after washing with an aqueous sodium hydrogen carbonate solution, distilled water and saturated brine, the organic layer was concentrated. The obtained oily product was purified by column chromatography to obtain 33.4 parts by mass of an alicyclic olefin compound (2-2) having the following structure.

Compound (2-2)

上記で得られた白色固体化合物（２−１）９．２質量部、炭酸カリウム７．６質量部、ＤＭＡｃ５０質量部を室温で攪拌しているところに、脂環オレフィン化合物（２−２）１３．２質量部を加え、８０℃に昇温して２時間反応させた。反応液に酢酸エチルを２００質量部加え、蒸留水、飽和食塩水で洗浄後、有機層を濃縮した。得られたオイル状生成物をカラムクロマトグラフィーで精製することにより、下記構造の脂環オレフィン化合物（２−３）１９．１質量部を得た。

While stirring 9.2 parts by weight of the white solid compound (2-1) obtained above, 7.6 parts by weight of potassium carbonate, and 50 parts by weight of DMAc at room temperature, the alicyclic olefin compound (2-2) 13 .2 parts by mass was added, the temperature was raised to 80 ° C., and the reaction was carried out for 2 hours. 200 parts by mass of ethyl acetate was added to the reaction solution, washed with distilled water and saturated brine, and the organic layer was concentrated. The obtained oily product was purified by column chromatography to obtain 19.1 parts by mass of an alicyclic olefin compound (2-3) having the following structure.

Compound (2-3)

続いて、上記の脂環オレフィン化合物（２−３）１９．１質量部を、合成例１と同様にｍ−クロロ過安息香酸を用いてエポキシ化をすることで、油状の下記重合性化合物（Ａ−１７）を２０．４質量部得た。

Subsequently, 19.1 parts by mass of the alicyclic olefin compound (2-3) was epoxidized using m-chloroperbenzoic acid in the same manner as in Synthesis Example 1 to obtain the following oily polymerizable compound ( 20.4 parts by mass of A-17) was obtained.

<Synthesis Example 3>
A mixed solution of 23.2 parts by mass of cis-cyclohexanedicarboxylic anhydride, 41 parts by mass of methyl ethyl ketone, and 18.0 parts by mass of 3-cyclohexene-1-methanol was reacted at 80 ° C. for 24 hours with stirring. By concentrating and drying the reaction solution, 42.0 parts by mass of the alicyclic olefin compound (3-1) was obtained.

Compound (3-1)

上記で合成した脂環オレフィン化合物（３−１）を１３．３質量部、炭酸カリウム７．６質量部、ＤＭＡｃ５０質量部を室温で攪拌しているところに、合成例２で合成した脂環オレフィン化合物（２−２）１３．２質量部を加え、８０℃に昇温して２時間反応させた。反応液に酢酸エチルを２００質量部加え、蒸留水、飽和食塩水で洗浄後、有機層を濃縮した。得られたオイル状生成物をカラムクロマトグラフィーで精製することにより、下記構造の脂環オレフィン化合物（３−２）１６．３質量部を得た。

The alicyclic olefin compound synthesized in Synthesis Example 2 was prepared by stirring 13.3 parts by mass of the alicyclic olefin compound (3-1) synthesized above, 7.6 parts by mass of potassium carbonate, and 50 parts by mass of DMAc at room temperature. 13.2 parts by mass of the compound (2-2) was added, and the temperature was raised to 80 ° C. and reacted for 2 hours. 200 parts by mass of ethyl acetate was added to the reaction solution, washed with distilled water and saturated brine, and the organic layer was concentrated. The obtained oily product was purified by column chromatography to obtain 16.3 parts by mass of an alicyclic olefin compound (3-2) having the following structure.

Compound (3-2)

続いて、上記の脂環オレフィン化合物（３−２）１６．３質量部を、合成例１と同様にｍ−クロロ過安息香酸を用いてエポキシ化をすることで、油状の下記重合性化合物（Ａ−２２）を１７．２質量部得た。

Subsequently, 16.3 parts by mass of the alicyclic olefin compound (3-2) was epoxidized using m-chloroperbenzoic acid in the same manner as in Synthesis Example 1 to obtain the following oily polymerizable compound ( 17.2 parts by mass of A-22) was obtained.

<Synthesis Example 4>
29.7 parts by mass of triglycidyl isocyanurate (manufactured by Nissan Chemical Co., Ltd., TEPIC-S) and 12.6 parts by mass of dimethylhydantoin (manufactured by Mitsui Chemicals Fine Co., Ltd., 55DMH) are melted at 150 ° C. and stirred. The reaction was continued for 1 hour. The product was taken out from the flask and allowed to cool to room temperature to obtain an oligomer having a melting point of 70 ° C.

Preparation of photosensitive resin composition for optical waveguide The components shown in Table 1 below were stirred and mixed to obtain uniform transparent resin compositions (compositions 1 to 17).

<Example 1>
Using composition 1, the following heat resistance and refractive index were evaluated. The results are summarized in Table 1.

[Heat-resistant]
A composition obtained by applying the composition 1 on a silicon substrate by spin coating so that the film thickness after curing becomes 20 μm and curing by ultraviolet irradiation (24 J / cm ² ) is cut out into a strip shape together with the substrate. It was immersed in a solder bath at 280 ° C. for 30 seconds, and the cured product was visually evaluated. The case where there was no peeling or swelling was designated as heat resistance ○, and the case where peeling or swelling occurred was designated as heat resistance ×.

[Refractive index]
Refraction at a wavelength of 850 nm by a prism coupler method using a sample obtained by applying composition 1 on a silicon substrate by spin coating so that the film thickness after curing is 10 μm and curing by ultraviolet irradiation (24 J / cm ² ). The rate was measured.

<Examples 2 to 11>
In the same manner as in Example 1, the heat resistance and refractive index were evaluated using Compositions 2 to 11, respectively. The results are summarized in Table 1.

<Comparative Examples 1-6>
In the same manner as in Example 1, the above-described heat resistance and refractive index were evaluated using Compositions 12 to 17, respectively. The results are summarized in Table 1.

As is apparent from Table 1, the compositions 1 to 11 (Examples 1 to 11) containing the polymerizable compound (A) of the present invention have good solder heat resistance and are sufficiently refracted to produce an optical waveguide. It became possible to get the rate one. Moreover, as is clear from the compositions 1 to 11 (Examples 1 to 11), the refractive index can be adjusted by employing the polymerizable compound (A) in combination with other alicyclic epoxy compounds. It was. By this adjustment, it becomes possible to increase the refractive index as compared with the compositions 13, 16, and 17 (for example, Comparative Examples 2, 5, and 6) using the conventional alicyclic epoxy compound. In particular, the present invention is extremely advantageous in that the refractive index can be increased without deteriorating solder heat resistance.
As described above, in the conventional techniques (Comparative Examples 1 to 6), it is difficult to achieve both solder heat resistance and high refractive index, and the photosensitive resin compositions for the core layer and the clad layer both have high heat resistance. Although it was not obtained, in the present invention, it became clear that a photosensitive resin composition for a high heat resistant core layer and a high heat resistant clad layer can be obtained. And since it became possible to set it as such a structure, there exists an advantage that the optical waveguide suitable for the optical / electrical composite printed wiring board etc. with which high heat resistance is requested | required can be produced simply.

<Example 12>
The composition 16 is applied on a silicon substrate by spin coating so that the film thickness after curing is 50 μm, and the entire surface is irradiated with ultraviolet rays (24 J / cm ² ) and cured to produce a lower cladding layer. did. Next, the composition 1 is applied onto the lower clad layer by spin coating so that the film thickness after curing is 50 μm, and ultraviolet rays are passed through a mask having a linear waveguide pattern with a width of 50 μm. Was cured by irradiation (24 J / cm ² ). Then, when this sample was developed with an organic solvent and air-dried, a core layer having a width of 50 μm and a film thickness of 50 μm could be produced. Further, the composition 16 is applied onto the core layer and the lower cladding layer by spin coating so that the film thickness after curing (film thickness from the lower cladding layer) becomes 100 μm, and the entire surface is irradiated with ultraviolet rays ( 24 J / cm ² ) and cured to prepare an upper clad layer.
Using the obtained optical waveguide, propagation loss and heat resistance of the optical waveguide were evaluated. The results are summarized in Table 2.

[Propagation loss of optical waveguide]
The optical waveguide was cut out by dicing, and the propagation loss of optical waveguides having different lengths was measured by the cutback method. For the measurement, a laser having a wavelength of 850 nm was used. A propagation loss of less than 0.5 dB / cm was evaluated as ◯, 0.5 dB / cm to 1.0 dB / cm as Δ, and a value exceeding 1.0 dB / cm as ×.

[Heat resistance of optical waveguide]
The optical waveguide was cut out by dicing, and optical waveguides having different lengths were heat-treated at 250 ° C. for 30 seconds, and then the propagation loss was measured by a cutback method. The change of the propagation loss before and after the heat treatment was evaluated as “◯” when less than 0.5 dB / cm, “Δ” when 0.5 dB / cm to 1.0 dB / cm, and “×” when exceeding 1.0 dB / cm.

<Examples 13 to 15>
An optical waveguide was produced in the same manner as in Example 12 except that the composition 1 in Example 12 was changed to the compositions 3, 4, and 6, and propagation loss and heat resistance of the optical waveguide were evaluated. . The results are summarized in Table 2.

<Example 16>
An optical waveguide was produced in the same manner as in Example 12 except that the composition 16 in Example 12 was changed to the composition 2, and propagation loss and heat resistance of the optical waveguide were evaluated. The results are summarized in Table 2.

<Examples 17 to 19>
An optical waveguide was produced in the same manner as in Example 12 except that the composition 16 in Example 12 was changed to the composition 17 and the composition 1 was changed to the compositions 7, 8, and 9, respectively. Propagation loss and heat resistance were evaluated. The results are summarized in Table 2.

<Example 20>
An optical waveguide was produced in the same manner as in Example 12 except that the composition 16 in Example 12 was changed to the composition 10 and the composition 1 was changed to the composition 7, and propagation loss and heat resistance of the optical waveguide were improved. Evaluation was performed. The results are summarized in Table 2.

<Comparative Examples 7-9>
An optical waveguide was produced in the same manner as in Example 12 except that the composition 1 in Example 12 was changed to compositions 12, 14, and 15, respectively, and propagation loss and heat resistance of the optical waveguide were evaluated. The results are summarized in Table 2.

As can be seen from Table 2, when the photosensitive resin composition for an optical waveguide of the present invention is used for at least the core layer (Examples 12 to 20), it is possible to achieve both propagation loss and heat resistance of the optical waveguide. It was.
On the other hand, when the photosensitive resin composition for optical waveguides of the present invention was not used for the core layer, the propagation loss of the optical waveguides was slightly inferior, and the heat resistance was worse (Comparative Examples 7 to 9).
In addition, when the polymerizable compound contained in the photosensitive resin composition for an optical waveguide of the present invention is used for both the core layer and the clad layer, the photosensitive resin composition for an optical waveguide composed only of an alicyclic epoxy compound (implementation) Examples 17-20), it was observed that there is the advantage that the change in propagation loss before and after heat treatment is very small.

  The photosensitive resin composition for optical waveguides of the present invention can be used for production of optical waveguides. Further, the refractive index adjusting agent of the present invention is effective for adjusting the refractive index of an optical waveguide formed by curing an alicyclic epoxy polymerizable compound, particularly for increasing the refractive index.

FIG. 1 is a schematic view showing an example of a method for manufacturing an optical waveguide according to the present invention.

Explanation of symbols

1 Board
2 Photosensitive resin composition for lower clad layer
3 light
4 Lower cladding layer
5 Photosensitive resin composition (for core layer) of the present invention
6 Photomask
7 Core layer
8 Photosensitive resin composition for upper clad layer
9 Upper cladding layer
10 Optical waveguide

Claims (8)

(A) The photosensitive resin composition for optical waveguides which contains the polymeric compound which has at least 2 or more alicyclic epoxy groups in a molecule | numerator, and contains at least 1 or more aromatic ring in a molecule | numerator. The photosensitive resin composition for optical waveguides according to claim 1, wherein the polymerizable compound (A) is represented by the following general formula (1).
General formula (1)

(In the general formula (1), E ¹¹ and E ¹² each represent an alicyclic epoxy group. R ¹¹ and R ¹² each represent a single bond, a divalent aliphatic hydrocarbon group, or a divalent aroma. A ¹¹ and A ¹² each represent a single bond, or —SO—, —SO ₂ —, —CO—, —O—, —S—, —N (R ¹³ ) — (R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), and a group composed of a combination thereof, Ar ¹¹ represents a divalent aromatic hydrocarbon group, and a and c are each 1 Represents an integer of ˜3, b represents an integer of 0 to 3. When b = 0, at least one of E ¹¹ and E ¹² represents an alicyclic epoxy group having a substituent containing an aromatic ring. .) The photosensitive resin composition for an optical waveguide according to claim 1, further comprising (B) a photoacid generator. The optical waveguide which has a core layer and a clad layer, and the said core layer consists of hardened | cured material of the photosensitive resin composition for optical waveguides of any one of Claims 1-3. An optical waveguide having a core layer and a clad layer, wherein both the core layer and the clad layer are made of a cured product of a photosensitive resin composition for an optical waveguide containing only an alicyclic epoxy compound as a polymerizable compound. The said core layer is an optical waveguide of Claim 5 which consists of hardened | cured material of the photosensitive resin composition for optical waveguides of any one of Claims 1-3. A refractive index adjuster for an optical waveguide obtained by curing an alicyclic epoxy polymerizable compound, (A) having at least two alicyclic epoxy groups in the molecule, and at least one in the molecule A refractive index adjusting agent comprising a polymerizable compound containing an aromatic ring. A method for adjusting the refractive index of an optical waveguide obtained by curing an alicyclic epoxy polymerizable compound, wherein (A) the molecule has at least two alicyclic epoxy groups in the molecule, and at least one in the molecule. The refractive index adjustment method including using the polymeric compound containing the aromatic ring of this.

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