JP2005092104A - Polymer optical waveguide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer optical waveguide at a low cost having a core form accurately reproducing the objective form and having excellent heat resistance. <P>SOLUTION: The polymer optical waveguide has a core layer and a clad layer on a substrate. The core layer is made of a photosensitive resin composition containing, as the proportion of each component with respect to the whole composition, 10 to 30 wt.% dimethacrylate, 30 to 50 wt.% mono(meth)acrylate, 5 to 10 wt.% (meth)acrylate having six (meth)acryloyl groups in the molecule, 10 to 20 wt.% monomethacrylate having an alicyclic structure, and a photo-radical polymerization initiator as the structural components. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polymer optical waveguide produced using a photosensitive resin composition for forming an optical waveguide.

  Quartz has often been used as a material for optical waveguides. Quartz waveguides have excellent properties such as high heat resistance, low polarization dependence, low loss, and low temperature dependence of refractive index, but they include high temperature processes and reactive ion etching (RIE) processes. The disadvantage is that the processability is low, and the processability is inferior. Therefore, polymer waveguides have been studied from the viewpoint of productivity and workability.

  Polymer waveguide is a reactive ion etching (RIE) method, after applying a photocurable material, irradiating the core with ultraviolet light and removing the unirradiated portion by development (direct exposure method) (Patent Document 1), a stamper method (Patent Document 2), and the like have been studied. In the RIE method, after forming a thin film, a resist is applied, UV exposure is performed, a pattern is formed by development, and a portion not covered with the resist is scraped by RIE. Thereafter, a step of removing the resist is required. Since there are a vacuum process and a resist process at the time of RIE, there is a disadvantage that the number of processes is generally large. In addition, there is a drawback in that scattering loss increases due to the creation of minute vertical flaws on the side surface of the core by RIE. Further, when a multimode waveguide having a large core diameter is manufactured, it takes time for RIE, resulting in high cost, and it cannot be said that it is an optimum method for manufacturing a waveguide having a core diameter of 20 μm or more.

  The stamper method is an excellent process for mass production in which a concave groove is formed by a stamper, and then a resin is poured into the groove to form a core, so that low cost can be realized. However, it is difficult to form the side surface portion of the groove, and the current situation is that sufficient waveguide efficiency is not obtained due to generation of voids, flash during overcladding production, and the like. Moreover, it is difficult to produce a core having a thickness of 20 μm to 90 μm using a stamper. On the other hand, the direct exposure method does not have a step of covering with a resist, and a pattern can be produced by removing the unexposed portion by development after direct exposure to ultraviolet rays (UV), so the number of steps can be reduced compared to RIE. It is low-cost and can suppress scattering loss due to side surface fluctuations as seen in RIE and stampers. Moreover, a waveguide having a core diameter of 20 to 90 μm, which has been difficult with a mold or the like because a waveguide having a wide range of core diameters can be manufactured, can be easily manufactured. However, when a plurality of cores are produced, if the core interval is narrow, there is a problem that the space between the cores is buried due to the scattered light of UV irradiated to each core.

  Examples of the material for the polymer waveguide include fluorinated polyimide, epoxy, and acrylic, but acrylic materials are relatively inexpensive and excellent in transparency.

Japanese Patent Laid-Open No. 2001-4858 JP-A-8-327844

  However, acrylic materials have a problem that heat resistance is poor, and there is a problem that polymerization is inhibited by oxygen when performing a direct exposure method.

  In addition, resolution is important when manufacturing waveguides with branched shapes and integrated waveguides, but the resolution is degraded by the direct exposure method due to scattered light and diffracted light from the mask pattern. There is.

  In order to avoid the influence of oxygen inhibition, measures are taken such as increasing the amount of the initiator, using an initiator having a high surface curability, filling with nitrogen and irradiating UV. However, when curing under nitrogen is more costly than under air, resolution is reduced, and when a multimode waveguide with a film thickness is made with a highly surface-curing initiator, the waveguide There is a problem that UV absorption is large on the surface and the core on the UV irradiation side is thick, and conversely, the substrate side is thin and the shape of the waveguide cross section is not good.

  As described above, conventional acrylic materials have problems with respect to heat resistance, patternability, and the like, and polymer optical waveguides manufactured using them have not satisfied various characteristics required for waveguides.

  Therefore, the present invention is to provide a polymer optical waveguide having a core shape that accurately reproduces a target shape and having excellent heat resistance at low cost.

  As a result of intensive studies in order to solve the above problems, the present inventor has made a polymer prepared from a photosensitive resin composition containing an acrylate having a specific structure and two or more types of photoradical polymerization initiators having different absorption wavelengths. The present invention was completed by finding that the optical waveguide has good characteristics.

That is, the present invention is a polymer optical waveguide having a core layer and a clad layer on a substrate, and the core layer has the following components (A) to (E) as the content of each component relative to the total amount of the composition:
(A) 10 to 30% by weight of dimethacrylate having a structure represented by the following chemical formula 1,

（式中、Ｒ¹は、−（ＯＣＨ₂ＣＨ₂）_m―、―（ＯＣＨ（ＣＨ₃）ＣＨ₂）_m―、
または、―ＯＣＨ₂ＣＨ（ＯＨ）ＣＨ₂−；
Ｘは、−Ｃ（ＣＨ₃）₂−、−ＣＨ₂−、−Ｏ−または−ＳＯ₂−；Ｙは、水素原子またはハロゲン原子；ｍは、０〜４の整数を表す。）、
（Ｂ）下記化２で表される構造を有するモノ（メタ）アクリレート ３０〜５０重量％、

(Wherein R ¹ represents — (OCH ₂ CH ₂ ) _m —, — (OCH (CH ₃ ) CH ₂ ) _m —,
Or —OCH ₂ CH (OH) CH ₂ —;
X represents —C (CH ₃ ) ₂ —, —CH ₂ —, —O— or —SO ₂ —; Y represents a hydrogen atom or a halogen atom; m represents an integer of 0 to 4. ),
(B) 30 to 50% by weight of mono (meth) acrylate having a structure represented by the following chemical formula 2

（式中、Ｒ²は、−（ＯＣＨ₂ＣＨ₂）_p―、―（ＯＣＨ（ＣＨ₃）ＣＨ₂）_p―、
または、―ＯＣＨ₂ＣＨ（ＯＨ）ＣＨ₂−；
Ｙは、水素原子、ハロゲン原子、Ｐｈ−Ｃ（ＣＨ₃）₂−、Ｐｈ−、または、炭素数１〜２０のアルキル基；ｐは０〜４の整数を表す。ただし、Ｐｈは、フェニル基を表す。）、
（Ｃ）（メタ）アクリロイル基を分子中に６個有する（メタ）アクリレート ５〜１０重量％、
（Ｄ）脂環構造を有するモノアクリレート １０〜２０重量％、
および
（Ｅ）下記の光ラジカル重合開始剤（Ｅ１）および（Ｅ２）、（Ｅ１）と（Ｅ２）の合計量として１〜５重量％、但し、成分（Ｅ１）１００重量％に対する成分（Ｅ２）の量は１５〜３０重量％である、
（Ｅ１）下記化３で表される構造を有する光ラジカル重合開始剤、

(Wherein R ² represents — (OCH ₂ CH ₂ ) _p —, — (OCH (CH ₃ ) CH ₂ ) _p —,
Or —OCH ₂ CH (OH) CH ₂ —;
Y represents a hydrogen atom, a halogen atom, Ph—C (CH ₃ ) ₂ —, Ph—, or an alkyl group having 1 to 20 carbon atoms; p represents an integer of 0 to 4. However, Ph represents a phenyl group. ),
(C) 5 to 10% by weight of (meth) acrylate having 6 (meth) acryloyl groups in the molecule,
(D) 10-20% by weight of monoacrylate having an alicyclic structure,
And (E) 1 to 5% by weight as a total amount of the following photo radical polymerization initiators (E1) and (E2), (E1) and (E2), provided that component (E2) is 100% by weight of component (E1) The amount of is 15-30% by weight,
(E1) a radical photopolymerization initiator having a structure represented by the following chemical formula 3,

（式中、Ｒ³は有機基、Ｒ₄は水素原子又は水酸基を表す。）、
（Ｅ２）下記化４で表される構造を有する光ラジカル重合開始剤、

(Wherein R ³ represents an organic group, R ₄ represents a hydrogen atom or a hydroxyl group),
(E2) a radical photopolymerization initiator having a structure represented by the following chemical formula 4:

(In the formula, R ⁵ represents an organic group having a nitrogen atom.)
Is a polymer optical waveguide having a branched shape and a thickness of 20 to 90 μm.

  With the polymer optical waveguide of the present invention, it is possible to provide a polymer optical waveguide having excellent cost and mass productivity, practical heat resistance, and excellent shape.

  The best mode of the present invention will be described below.

  Component (A) is dimethacrylate having a structure represented by Chemical Formula 1.

（式中、Ｒ¹は、−（ＯＣＨ₂ＣＨ₂）_m―、―（ＯＣＨ（ＣＨ₃）ＣＨ₂）_m―、または、―ＯＣＨ₂ＣＨ（ＯＨ）ＣＨ₂−；Ｘは−Ｃ（ＣＨ₃）₂−、−ＣＨ₂−、−Ｏ−、または、−ＳＯ₂−；Ｙは、水素原子またはハロゲン原子；ｍは０〜４の整数を表す。）。

(Wherein R ¹ represents — (OCH ₂ CH ₂ ) _m —, — (OCH (CH ₃ ) CH ₂ ) _m —, or —OCH ₂ CH (OH) CH ₂ —; X represents —C (CH ₃ ) ₂ —, —CH ₂ —, —O—, or —SO ₂ —; Y represents a hydrogen atom or a halogen atom; m represents an integer of 0 to 4).

  In the above formula (1), examples of the halogen atom represented by Y include chlorine, bromine, iodine, and fluorine. Of these, bromine is preferable.

  Specific examples of the component (A) include, for example, ethylene oxide-added bisphenol A methacrylate, ethylene oxide-added tetrabromobisphenol A methacrylate, propylene oxide-added bisphenol A methacrylate, propylene oxide-added tetrabromobisphenol A methacrylate. Acrylic acid ester, bisphenol A epoxyglycacrylate obtained by epoxy ring-opening reaction of bisphenol A diglycidyl ether and methacrylic acid, tetrabromo obtained by epoxy ring-opening reaction of tetrabromobisphenol A diglycidyl ether and methacrylic acid Bisphenol A obtained by epoxy ring-opening reaction of bisphenol A epoxy methacrylate, bisphenol F diglycidyl ether and methacrylic acid Lumpur F epoxy methacrylate, tetrabromobisphenol F epoxy methacrylate obtained by an epoxy ring-opening reaction of tetrabromobisphenol F diglycidyl ether with methacrylic acid and the like.

  Among them, ethylene oxide-added bisphenol A methacrylate, ethylene oxide-added tetrabromobisphenol A methacrylate, bisphenol A epoxy methacrylate obtained by epoxy ring-opening reaction of bisphenol A diglycidyl ether and methacrylic acid, tetrabromobisphenol A Epoxy methacrylate and the like are particularly preferably used.

  As a commercial item of component (A), for example, Biscote # 700, # 540 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), Aronix M-208, M-210 (above, manufactured by Toagosei Co., Ltd.), NK ester BPE-100, BPE-200, BPE-500, A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.), light ester BP-4EA, BP-4PA, epoxy ester 3002M, 3002A, 3000M, 3000A (Made by Kyoeisha Chemical Co., Ltd.), KAYARAD R-551, R-712 (Made by Nippon Kayaku Co., Ltd.), BPE-4, BPE-10, BR-42M (Made by Daiichi Kogyo Pharmaceutical Co., Ltd.) Manufactured by Co., Ltd.), Lipoxy VR-77, VR-60, VR-90, SP-1506, SP-1506, SP-1507, SP-1509, SP-1563 (above, Sum polymer Co., Ltd.), NEOPOL V779, NEOPOL V779MA (manufactured by Japan U-PICA Co., Ltd.), and the like.

  The weight ratio of the component (A) in the photosensitive resin composition of the present invention is 10 to 30% by weight based on the total amount of the composition.

  When the weight ratio is less than 10% by weight or more than 30% by weight, it is difficult to achieve both transmission characteristics, mechanical properties of the cured product, and heat resistance.

  Component (B) is a mono (meth) acrylate having a structure represented by Chemical Formula 2.

（式中、Ｒ²は、−（ＯＣＨ₂ＣＨ₂）_p―、―（ＯＣＨ（ＣＨ₃）ＣＨ₂）_p―、または、―ＯＣＨ₂ＣＨ（ＯＨ）ＣＨ₂−；Ｙは、水素原子、ハロゲン原子、Ｐｈ−Ｃ（ＣＨ₃）₂−、Ｐｈ−、または炭素数１〜２０のアルキル基；ｐは０〜４の整数を表す。ただし、Ｐｈは、フェニル基を表す。）、
なお、上記式（２）中、Ｙが表すハロゲン原子としては、塩素、臭素、ヨウ素、フッ素等が挙げられる。中でも、臭素が好ましい。

(Wherein R ² represents — (OCH ₂ CH ₂ ) _p —, — (OCH (CH ₃ ) CH ₂ ) _p —, or —OCH ₂ CH (OH) CH ₂ —; Y represents a hydrogen atom; A halogen atom, Ph—C (CH ₃ ) ₂ —, Ph—, or an alkyl group having 1 to 20 carbon atoms; p represents an integer of 0 to 4, provided that Ph represents a phenyl group.
In the above formula (2), examples of the halogen atom represented by Y include chlorine, bromine, iodine, and fluorine. Of these, bromine is preferable.

  Specific examples of the component (B) include, for example, phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, and 3-phenoxy-2-hydroxypropyl (meth) acrylate. 2-phenylphenoxyethyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, p-cumylphenol ethylene oxide modified (meth) acrylate, 2-bromophenoxy Ethyl (meth) acrylate, 4-bromophenoxyethyl (meth) acrylate, 2,4-dibromophenoxyethyl (meth) acrylate, 2,6-dibromophenoxyethyl (meth) acrylate, 2,4,6 Tribromophenoxyethyl (meth) acrylate.

  Among them, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, (meth) acrylate of p-cumylphenol reacted with ethylene oxide, 2,4,6-tribromophenoxyethyl (meth) acrylate, Particularly preferably used.

  As a commercial item of component (B), for example, Aronix M113, M110, M101, M102, M5700, TO-1317 (above, manufactured by Toagosei Co., Ltd.), Biscote # 192, # 193, # 220, 3BM (above , Osaka Organic Chemical Industry Co., Ltd.), NK Ester AMP-10G, AMP-20G (above, Shin-Nakamura Chemical Co., Ltd.), Light Acrylate PO-A, P-200A, Epoxy Ester M-600A (above Kyoeisha Chemical Co., Ltd.), PHE, CEA, PHE-2, BR-30, BR-31, BR-31M, BR-32 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like.

  The weight ratio of the component (B) in the photosensitive resin composition of the present invention is 30 to 50% by weight with respect to the total amount of the composition. When the weight ratio is less than 30% by weight or exceeds 50% by weight, it becomes difficult to achieve both transmission characteristics, mechanical properties of the cured product, and heat resistance.

  Component (C) is a (meth) acrylate having 6 (meth) acryloyl groups in the molecule.

  Specific examples of the component (C) include dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, alkyl-modified dipentaerythritol hexa (meth) acrylate, and commercially available products include KAYARAD. Examples include DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

  The weight ratio of the component (C) in the photosensitive resin composition of the present invention is 5 to 10% by weight with respect to the total amount of the composition.

  If the weight ratio is less than 5% by weight, sufficient mechanical properties and good patterning shape cannot be obtained, and conversely if it exceeds 10% by weight, the transmission characteristics may be deteriorated.

  Component (D) is a monoacrylate having an alicyclic structure.

  Specific examples of component (D) include cyclohexyl acrylate, isobornyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, dicyclopentanyl acrylate and the like, and commercially available products include light acrylate IB-XA, THF-A. (Above, Kyoeisha Chemical Co., Ltd.), Biscote # 155, # 150, IBXA (above, Osaka Organic Chemical Industry Co., Ltd.), KAYARAD T110S (Nippon Kayaku Co., Ltd.), FA-513A (Hitachi Chemical Co., Ltd.) Manufactured) and the like.

  The weight ratio of the component (D) in the photosensitive resin composition of the present invention is 10 to 20% by weight with respect to the total amount of the composition.

  If it is out of the weight ratio, transmission characteristics and mechanical characteristics deteriorate.

  Component (E) is a radical photopolymerization initiator. The radical photopolymerization initiator is not particularly limited.

  However, in order to obtain sufficient patterning properties, a photo radical polymerization initiator (E1) having a structure represented by the following chemical formula 3 and a photo radical polymerization initiator (E2) having a structure represented by the following chemical formula 4, It is necessary to use the component (E2) in an amount of 15 to 30% by weight based on 100% by weight of the component (E1). When the amount of the component (E2) is less than 15% by weight relative to 100% by weight of the component (E1), the surface curability decreases, and when it exceeds 30% by weight, the internal curing becomes insufficient, and both are sufficient. Patternability cannot be obtained.

（式中、Ｒ³は有機基、Ｒ⁴は水素原子又は水酸基を表す。）

(In the formula, R ³ represents an organic group, and R ⁴ represents a hydrogen atom or a hydroxyl group.)

（式中、Ｒ⁵は窒素原子を有する有機基を表す。）

(In the formula, R ⁵ represents an organic group having a nitrogen atom.)

  Specific examples of the photo radical polymerization initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-dimethoxy-2-phenylacetophenone, xanthone, benzaldehyde, triphenylamine, 3-methylacetophenone, 4- Chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 -One, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, xanthone, fluore , Fluorene, anthraquinone, carbazole, Michler ketone, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, Examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.

  Examples of commercially available radical photopolymerization initiators include Irgacure 184, 651, 500, 2959, 369, 819, 907, 784, Darocur 116, 1173, CGI 1700, CGI 1750, CGI 11850 (above, manufactured by Ciba Specialty Chemicals), Lucirin LR8728 (made by BASF) etc. are mentioned.

  The weight ratio of the component (E) in the photosensitive resin composition of the present invention is 1 to 5% by weight with respect to the total amount of the composition.

  If the weight ratio is less than 1% by weight, sufficient mechanical properties and good patterning shape cannot be obtained. Conversely, if it exceeds 5% by weight, transmission characteristics and long-term reliability may be deteriorated.

  In the present invention, as an optional component, in addition to the components (A) to (E), a compound containing a (meth) acryloyl group or a vinyl group (hereinafter also referred to as “unsaturated monomer”. However, the component ( A) to the same compound as component (E) can be used.

  Specific examples of these unsaturated monomers include, for example, vinyl monomers such as N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, and vinylpyridine; isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meta ) Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethyl (meth) ) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (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, tetrahydrofurfuryl (Meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxy Polyethylene 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, 7-amino-3,7-dimethyloctyl (Meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, hydroxybutyl building ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, 1,4-butanediol di Polyalkylene glycols such as acrylates, alkyldiol diacrylates such as 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate Diacrylate, neopentyl glycol di (meth) acrylate, tricyclodecane methanol diacrylate, trimethylolpropane tri (meth) acrylate Over DOO, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (2-acryloyloxyethyl) isocyanurate, pentaerythritol polyacrylate, and ditrimethylolpropane tetraacrylate.

  Specific examples of commercially available products of these compounds include, for example, Aronix M120, M-150, M-156, M-215, M-220, M-225, M-240, M-245, M-270, M305, M309, M310, M315, M320, M350, M360, M408 (above, manufactured by Toagosei Co., Ltd.), AIB, TBA, LA, LTA, STA, Biscote # 158, # 190, # 320, HEA, HPA, Biscote # 2000, # 2100, DMA, Biscote # 195, # 230, # 260, # 215, # 335HP, # 310HP, # 310HG, # 312, # 295, # 300, # 360, GPT, 3PA, # 400 (and above) Osaka Organic Chemical Co., Ltd.), Light Acrylate IAA, LA, SA, BO-A, EC-A, MTG A, DMP-A, THF-A, HOA, HOP-A, HOA-MPL, HOA-MPE, light acrylate 3EG-A, 4EG-A, 9EG-A, NP-A, 1,6HX-A, DCP- A, TMP-A, TMP-6EO-3A, PE-3A, PE-4A (manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, PET -30, GPO-303, TMPTA, TPA-320 (above, Nippon Kayaku Co., Ltd.), VP (BASF), ACMO, DMAA, DMAPAA (above, Kojin Co., Ltd.), NK ester TMPT, A-TMPT, A-TMM-3, A-TMM-3L, A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like can be mentioned.

  The resin composition of the present invention may further contain an oligomer or polymer such as polyurethane (meth) acrylate, polyester (meth) acrylate, or polyepoxy (meth) acrylate.

  In the resin composition of the present invention, a photosensitizer can be further blended as necessary.

  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.

  In the present invention, various additives other than the above-mentioned components include, for example, antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, coating surface improvers, thermal polymerization inhibitors, leveling agents, and surface active agents. An agent, a colorant, a storage stabilizer, a plasticizer, a lubricant, a solvent, a filler, an antiaging agent, a wettability improving agent, a release agent, and the like can be blended as necessary.

  The resin composition of the present invention can be produced by mixing the above components by a conventional method. The viscosity of the resin composition of the present invention thus prepared 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. It is. If the viscosity is too high, coating unevenness and undulation will occur when the resin composition is applied to the substrate, or patterning properties 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.

  The cured product of the resin composition of the present invention obtained by curing with radiation preferably has the following physical properties.

  The cured product of the resin composition of the present invention preferably has a glass transition temperature of 100 ° C. or higher.

If the temperature is less than 100 ° C., sufficient heat resistance of the polymer optical waveguide may not be ensured.
By producing a polymer optical waveguide by the direct exposure method using the photosensitive resin composition, a polymer optical waveguide having low cost and excellent mass productivity can be provided.

  FIG. 1 shows a procedure for producing a polymer optical waveguide by the direct exposure method.

  After the clad material 2 is applied to the substrate 1 shown in FIG. 1 (a) (FIG. 1 (b)), it is cured by irradiation with UV3 as shown in FIG. 1 (c). Thereafter, as shown in FIG. 1 (d), the core material 4 is applied, UV is irradiated through the mask 5 as shown in FIG. 1 (e), and the developer is used as shown in FIG. 1 (f). The unexposed portion is removed, and the core portion 6 is formed by performing post exposure with UV3 as shown in FIG. After the core portion 6 is formed, a clad material 7 is applied as shown in FIG. 1 (h), and the clad material 7 is cured by irradiating UV3 again as shown in FIG. 1 (i). The waveguide is completed. The clad material 7 may be cured by heat.

  A general multimode fiber has a core diameter of 50 μm or 62.5 μm, and a polymer optical waveguide having a thickness of 20 to 90 μm is desirable for easy connection.

  Specifically, for example, as shown in FIG. 2, in order to receive the light emitted from the laser 16 by the polymer optical waveguide 15 and guide the light to the multimode fiber 14, the core diameter of the core 19 of the polymer optical waveguide 15 is determined by the laser. The waveguide needs to be larger than 16 beam diameters and smaller than the diameter of the multimode fiber 14, and a waveguide of 20 μm to 62.5 μm is suitable. At this time, if it is less than 20 μm, the ease of connection with the laser 16 becomes worse, and conversely if it is 62.5 μm or more, the loss increases.

  For example, as shown in FIG. 3, in order to receive light emitted from the multimode fiber 14 by the polymer optical waveguide 17 and guide the light to the light receiver 18, the core diameter of the core 20 of the polymer optical waveguide 17 is set to multimode. It must be larger than the diameter of the fiber 14 and smaller than the diameter of the light receiver 18, and a 62.5 μm to 90 μm waveguide is suitable. Also at this time, the loss increases if it is 62.5 μm or less, and conversely, if it is 90 μm or more, the ease of connection to the light receiver 18 is deteriorated.

  In addition, when performing light distribution and distribution, as shown in FIG. 4, a core 9 having a branched shape is necessary, and it is necessary to provide a polymer optical waveguide 12 having the branched core 9 at low cost. .

  In the polymer optical waveguide 12 having a core diameter of 20 to 90 μm, in order to reduce the loss at the branch portion, it is necessary to make the branch angle 13 as small as possible and make the branch portion as sharp as possible. By producing a polymer optical waveguide by faithfully reproducing the mask pattern of the branching portion interval 8 with the above material, a polymer optical waveguide 12 having a branched shape excellent in characteristics such as loss and heat resistance can be produced.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

  Each component described in Table 1 was charged and stirred for 1 hour while controlling the liquid temperature at 50 to 60 ° C. to obtain a liquid resin composition. In Table 1, the unit of addition amount of each component is parts by weight.

In Table 1,
V779MA: Neopole V779MA (manufactured by Nippon Yupica Co., Ltd.)
(Compound name: Tetrabromobisphenol A epoxy dimethacrylate)
PEMA: Light ester PO (manufactured by Kyoeisha Chemical Co., Ltd.)
(Compound name: Phenoxymethyl methacrylate)
BR-31: New Frontier BR-31 (Daiichi Kogyo Seiyaku Co., Ltd.)
(Compound name: Tribromophenoxyethyl acrylate)
DPHA: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
(Compound name: Dipentaerythritol hexaacrylate)
IBXA: Light ester IB-XA (manufactured by Kyoeisha Chemical Co., Ltd.)
(Compound name: Isobornyl acrylate)
IRG184: Irgacure 184 (Ciba Specialty Chemicals)
(Compound name: 1-hydroxy-cyclohexyl-phenyl ketone)
IRG369: Irgacure 369 (Ciba Specialty Chemicals)
(Compound name: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1)
V779: Neopole V779 (manufactured by Nippon Iupika Co., Ltd.)
(Compound name: Tetrabromobisphenol A epoxy diacrylate)
TMPTA: TMP-A (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
(Compound name: Trimethylolpropane triacrylate)
IRG651: Irgacure651 (Ciba Specialty Chemicals)
(Compound name: 2,2-dimethoxy-1,2-diphenylethane-1-one IRG907: Irgacure907 (manufactured by Ciba Specialty Chemicals)
(Compound name: 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

Example 1;
First, 2500 Clear made of photosensitive resin ELECTRO-LITE Corp was applied onto a silicon substrate by spin coating (FIG. 1B), and an under cladding layer having a thickness of 20 μm was formed by UV irradiation (FIG. 1C). . Next, the photosensitive resin composition shown in Table 1 was applied onto the undercladding layer by spin coating so that the thickness after curing was 60 μm (FIG. 1D), and the core width was 60 μm. As shown in FIG. 4, UV is irradiated through a mask having a Y-shaped pattern in which the distance 8 between the branching bases of the core 9 is 30 μm and the branching angle 13 is 1 ° (FIG. 1 (e)). The unirradiated portion was removed by (FIG. 1 (f)), and UV exposure was performed again (FIG. 1 (g)). Finally, 2500Clear made of photosensitive resin ELECTRO-LITE Corp was applied by spin coating (FIG. 1 (h)), and UV curing was performed to form an overcladding layer to produce a polymer optical waveguide (FIG. 1 (i)).

Example 2 and Comparative Examples 1-6
Polymer optical waveguides were produced by the same method except that each composition shown in Table 1 was used as the core layer.

  Next, the evaluation method of an Example and a comparative example is put together. The evaluation results are shown in Table 2.

<Evaluation method>
1. Evaluation of patterning property When a polymer optical waveguide 12 is produced based on Examples and Comparative Examples, a core having a target shape is obtained, and uncured portions between the cores are completely removed, and the design shape is ± 5 μm. "Double circle" for the case of having a shape, □ for the case of having a rectangular shape of design shape ± 10 μm, "○", if the core of the desired shape is not obtained or between the cores is filled with a core material " × ”.

2. Evaluation of Insertion Loss FIG. 5 shows a measurement system for the loss of the polymer optical waveguide 12 produced by the above process. The laser 10 was incident on one of the Y-shaped two sides of the core 9 and the light receiver 11 was placed on one Y-shaped side to evaluate the loss. When the insertion loss is 3.5 dB / cm or less, “double circle”, when larger than 3.5 dB / cm and 4.5 dB / cm or less, “◯”, when larger than 4.5 dB / cm, × ”.

3. Evaluation of heat resistance of polymer optical waveguide The glass transition temperature of the cured product was measured as an index of heat resistance evaluation. A 50 μm-thick coating film was formed with an applicator bar, and a cured coating film was prepared by UV irradiation. Then, the temperature change of the elasticity modulus of a coating film was measured using the dynamic viscoelasticity measuring apparatus, applying a vibration with a vibration frequency of 10 Hz. The loss tangent was calculated from the elastic modulus, and the temperature at which the loss tangent showed the maximum value was defined as the glass transition temperature (Tg). It was judged that good heat resistance was exhibited when the glass transition temperature was 100 ° C. or higher, and “X” when the glass transition temperature was lower than that.

  From the above evaluation, it was confirmed that Examples 1 and 2 had good patterning properties, insertion loss of 3.5 dB or less, and good heat resistance.

  On the other hand, although Comparative Example 1 has good patternability, the heat resistance is poor, Comparative Example 2 has poor heat resistance although the insertion loss is 3.5 dB or less, and Comparative Examples 3 to 6 are insertions. Although the loss was 3.5 dB or less and the heat resistance was good, the patterning property was poor.

  In the above-described embodiment, the example in which silicon is used as the substrate has been described. However, the material used as the substrate is not limited to silicon, and various materials such as quartz and polyimide can be used.

It is a figure which shows the procedure which produces a polymer optical waveguide in this invention. In the present invention, a laser and a multimode fiber are connected by a polymer optical waveguide. In the present invention, a light receiver and a multimode fiber are connected by a polymer optical waveguide. It is a figure which shows a Y branch waveguide in this invention. In this invention, it is a figure which shows the measurement system of the loss of a polymer optical waveguide.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Board | substrate 2 Clad 6 Core part 9 Core 12 Polymer optical waveguide 13 Branch angle 14 Multimode fiber 15 Polymer optical waveguide 16 Laser 17 Polymer optical waveguide 18 Light receiver

Claims (3)

A polymer optical waveguide having a core layer and a clad layer on a substrate, wherein the core layer contains the following components (A) to (E) as the content of each component relative to the total amount of the composition:
(A) 10 to 30% by weight of dimethacrylate having a structure represented by the following chemical formula 1

(Wherein R ¹ represents — (OCH ₂ CH ₂ ) _m —, — (OCH (CH ₃ ) CH ₂ ) _m —,
Or —OCH ₂ CH (OH) CH ₂ —;
X represents —C (CH ₃ ) ₂ —, —CH ₂ —, —O— or —SO ₂ —; Y represents a hydrogen atom or a halogen atom; m represents an integer of 0 to 4. ),
(B) 30 to 50% by weight of mono (meth) acrylate having a structure represented by the following chemical formula 2

(Wherein R ² represents — (OCH ₂ CH ₂ ) _p —, — (OCH (CH ₃ ) CH ₂ ) _p —,
Or —OCH ₂ CH (OH) CH ₂ —;
Y represents a hydrogen atom, a halogen atom, Ph—C (CH ₃ ) ₂ —, Ph—, or an alkyl group having 1 to 20 carbon atoms; p represents an integer of 0 to 4. However, Ph represents a phenyl group. ),
(C) 5 to 10% by weight of (meth) acrylate having 6 (meth) acryloyl groups in the molecule,
(D) 10-20% by weight of monoacrylate having an alicyclic structure,
And (E) 1 to 5% by weight as a total amount of the following photo radical polymerization initiators (E1) and (E2), (E1) and (E2), provided that component (E2) is 100% by weight of component (E1) The amount of is 15-30% by weight,
(E1) a radical photopolymerization initiator having a structure represented by the following chemical formula 3,

(Wherein R ³ represents an organic group, R ₄ represents a hydrogen atom or a hydroxyl group),
(E2) a radical photopolymerization initiator having a structure represented by the following chemical formula 4:

(In the formula, R ⁵ represents an organic group having a nitrogen atom.)
A polymer optical waveguide, which is made of a photosensitive resin composition containing as a constituent component.   2. The polymer optical waveguide according to claim 1, wherein the core diameter is 20 to 90 [mu] m. The polymer optical waveguide according to claim 1, wherein the core has a branched shape.

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