JP2008164854A - Film-like light waveguide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film-like light waveguide superior in curvature durability and electrification prevention. <P>SOLUTION: The film-like light waveguide has: a lower clad layer 10, a core part 18, and an upper clad layer 20; and electrification preventive layers 8, 22 on one or more surfaces of the lower clad layer 10 and the upper clad layer 20. The electrification preventive layers 8, 22 are a cured material of a composition containing (A) urethane (meta)acrylate oligomer, (B) a monomer having one or more (meta)acryloyl group in molecules, (C) an optical radical polymerization initiator, and (D) an electrification preventive agent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a film-shaped optical waveguide.

In the multimedia era, optical waveguides are attracting attention as optical transmission media because of the demand for large capacity and high speed information processing in optical communication systems and computers. A typical example of a conventional optical waveguide is a silica-based optical waveguide. However, silica-based optical waveguides require a long process time at a high temperature for the deposition of a quartz film at the time of manufacture. Etching with a high-risk gas is included, and special processes are required for these processes. Many complicated processes and special apparatuses are required, and the yield is low. There are problems such as.
In order to remedy these problems, liquid curability was developed as a material for the core and cladding layers, with the aim of improving productivity such as reducing the number of optical waveguide processes, shortening manufacturing time, and increasing yield. In recent years, polymer optical waveguides using the composition have been proposed.

  As an example of a polymer-based optical waveguide, (A) a structural unit having a side chain portion containing a radically polymerizable reactive group bonded via a urethane bond, and a structural unit having a side chain that is not polymerizable A copolymer comprising (B) a compound having one or more ethylenically unsaturated groups in the molecule, a molecular weight of less than 1,000, and a boiling point of 130 ° C. or higher at 0.1 MPa, and (C) A photosensitive resin composition for an optical waveguide containing a radical photopolymerization initiator has been proposed (Patent Document 1). When this photosensitive resin composition for optical waveguides is used, it is possible to form a polymer-based optical waveguide that has high shape accuracy and suppresses deterioration in transmission characteristics under high temperature and high humidity.

As a polymer-based optical waveguide using a liquid curable composition, development of a flexible film-shaped optical waveguide that has a thickness of less than 1 mm and does not cause breakage or cracking even when repeatedly bent is underway. In the field of optical interconnection, this film-shaped optical waveguide is connected to, for example, a surface emitting laser (VCSEL), which is a light emitting element, or a photodiode, which is a light receiving element, to convert electrical / optical signals. It is used as an optical transmission part in the interface.
JP 2006-146162 A

However, the film-shaped optical waveguide has a problem that it is easy to charge static electricity generated when the film-shaped optical waveguide is cut or handled. When a film-shaped optical waveguide with static electricity charged is used as the light transmission part of a light emitting / receiving element such as a surface emitting laser, the charged static electricity is discharged when the film-shaped optical waveguide is bonded to the light emitting / receiving element. Thus, a high voltage flows through the light emitting / receiving element at a time, and the light emitting / receiving element is likely to be damaged.
On the other hand, in order to prevent charging of the film-shaped optical waveguide, when an antistatic agent is contained in the curable composition that is a material of the core part or the clad layer, the component bleeds during heating, and the film-shaped optical waveguide This may cause problems such as a decrease in the reliability of the film, a decrease in the bending durability of the film-shaped optical waveguide, and a deterioration in optical characteristics due to light being easily scattered.
Then, an object of this invention is to provide the film-form optical waveguide excellent in antistatic property.

  As a result of intensive studies to solve the above problems, the present inventor has obtained an antistatic layer formed of a coating composition for an optical waveguide containing an antistatic agent, as a film-shaped optical waveguide including a core portion and a cladding layer. It has been found that if it is provided on at least one surface, excellent antistatic properties can be imparted, and the present invention has been completed. In addition, by using an antistatic layer formed of a coating composition for optical waveguides having a specific component composition containing an antistatic agent as the antistatic layer, the excellent bending durability of the film-like optical waveguide is maintained. The present inventors have found that excellent antistatic properties can be imparted.

The present invention provides the following [1] to [4].
[1] A film-shaped optical waveguide having a lower clad layer, a core portion, and an upper clad layer, wherein an antistatic layer is provided on at least one surface of the lower clad layer and the upper clad layer. Film-shaped optical waveguide.
[2] The film-like optical waveguide according to [1], wherein the antistatic layer is obtained by curing a composition containing the following components (A) to (D).
(A) Urethane (meth) acrylate oligomer (B) Monomer having one or more (meth) acryloyl groups in the molecule (C) Photoradical polymerization initiator (D) Antistatic agent [3] Said (D) antistatic The film-shaped optical waveguide according to [1] or [2], wherein the agent is at least one selected from the group consisting of a lithium-based antistatic agent, an ionic liquid antistatic agent, and a quaternary ammonium salt-based antistatic agent. .
[4] The film according to any one of [1] to [3], wherein the (A) urethane (meth) acrylate oligomer includes a reaction product of a polyol compound, a polyisocyanate compound, and a hydroxyl group-containing (meth) acrylate. Optical waveguide.

Since the film-like optical waveguide of the present invention has an antistatic layer on at least one (preferably both) of the lower clad layer and the upper clad layer, it receives light from a light emitting element such as a surface emitting laser or a photodiode. At the time of joining with the element, the light emitting element and the light receiving element are not damaged, and can be used as an optical interconnection having good transmission characteristics.
Moreover, the film-form optical waveguide of this invention can have the outstanding bending durability (bending resistance) by selecting suitably the material of the composition which forms an antistatic layer.

  The film-form optical waveguide of the present invention is a film-form optical waveguide having a lower clad layer, a core portion, and an upper clad layer, and an antistatic layer is provided on one or more surfaces of the lower clad layer and the upper clad layer. It is what you have. FIG. 1 is a sectional view schematically showing an example of the film-like optical waveguide of the present invention.

[Structure of film-shaped optical waveguide]
In FIG. 1, the film-shaped optical waveguide 24 has an antistatic layer 8, a lower clad layer 10 formed by being laminated on the upper surface of the antistatic layer 8, and a specific width formed on the upper surface of the lower clad layer 10. The upper clad layer 20 formed on the lower clad layer 10 and the core portion 18, and the antistatic layer 22 formed on the upper surface of the upper clad layer 20. .
The thicknesses of the lower cladding layer, the core portion, and the upper cladding layer are not particularly limited. For example, the thickness of the lower cladding layer is 1 to 200 μm, the thickness of the core portion is 3 to 200 μm, and the thickness of the upper cladding layer. Is determined to be 1 to 200 μm. Although the width | variety of a core part is not specifically limited, For example, it is 1-200 micrometers.
The refractive index of the core portion needs to be higher than any of the refractive indexes of the lower cladding layer and the upper cladding layer. For example, for light having a wavelength of 400 to 1,600 nm, the refractive index of the core portion is 1.420 to 1.650, the refractive indexes of the lower cladding layer and the upper cladding layer are 1.400 to 1.648, and The refractive index of the core portion is preferably at least 0.1% greater than the refractive index of any of the two cladding layers.
In FIG. 1, the film-like optical waveguide 24 is provided with the antistatic layers 8 and 10 on both surfaces. However, the present invention is not limited to this example, and the antistatic layer is bonded to a light emitting / receiving element such as a surface emitting laser. What is necessary is just to provide in the at least one surface of the film-form optical waveguide main body (what consists of a clad layer and a core part). However, it is preferable to provide an antistatic layer on both sides, as compared with the case where an antistatic layer is provided only on one side of the film-like optical waveguide, because the antistatic property and bending durability are improved.

The antistatic layer is for imparting excellent antistatic properties to the film-like optical waveguide.
Since the film-shaped optical waveguide has excellent antistatic properties, the film-shaped optical waveguide and the light emitting / receiving element can be joined to each other without damaging the light emitting / receiving element such as a surface emitting laser or a photodiode. Can be formed.
The surface resistivity of the antistatic layer is preferably 1 × 10 ¹² Ω / □ or less, more preferably 1 × 10 ¹¹ Ω / □ or less, and particularly preferably 1 × 10 ¹⁰ Ω / □ or less.
The film thickness (dry film thickness) in the dry state of the antistatic layer is preferably 1 to 100 μm, more preferably 3 to 50 μm, and particularly preferably 5 to 20 μm.

It is preferable that the antistatic layer has a suitable elasticity as well as excellent antistatic properties. Specifically, the Young's modulus of the antistatic layer is 550 to 750 MPa, preferably 570 to 730 MPa, more preferably 600 to 700 MPa. By setting the Young's modulus of the antistatic layer within the above range, a film-shaped optical waveguide having excellent bending durability can be obtained.
Moreover, it is preferable that an antistatic layer has moderate transparency. Specifically, the light transmittance of the antistatic layer is preferably 90% or more with respect to light having a wavelength of 365 nm. The antistatic layer has moderate transparency, so that a light emitting element such as a surface emitting laser or a light receiving element such as a photodiode is joined to the lower surface of the film-like optical waveguide to convert an electrical / optical signal. When forming, there is an advantage that the position of the light emitting element or the light receiving element can be accurately aligned with the position of the core portion in the film-shaped optical waveguide by seeing through the film-shaped optical waveguide from above.

Next, the coating composition for optical waveguides for forming the antistatic layer of the film-form optical waveguide of this invention is demonstrated. The coating composition for optical waveguides is composed of the following components (A) to (D) and other optional components (for example, the following component (E)).
[Component (A)]
Component (A) used in the present invention is a urethane (meth) acrylate oligomer.
Preferable examples of component (A) include an oligomer having a linear structure having a urethane bond repeatedly obtained by reacting a polyol compound and a polyisocyanate compound and having two or more (meth) acryloyl groups. It is done.
Component (A) is produced, for example, by reacting (c) a hydroxyl group-containing (meth) acrylate with (a) a polyol compound and (b) a polyisocyanate compound. Specifically, it is produced by any one of the following production methods 1 to 4.
Production method 1: A method in which a polyol compound, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate are charged and reacted together.
Production method 2: A method in which a polyol compound and a polyisocyanate compound are reacted and then a hydroxyl group-containing (meth) acrylate is reacted.
Production method 3: A method in which a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate are reacted, and then a polyol compound is reacted.
Production Method 4: A method in which a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate are reacted, then a polyol compound is reacted, and finally, a hydroxyl group-containing (meth) acrylate compound is reacted again.

Hereinafter, (a) polyol compound, (b) polyisocyanate compound, and (c) hydroxyl group-containing (meth) acrylate used for the production of component (A) will be described in detail.
[(A) Polyol compound]
(A) As a polyol compound, aliphatic polyether polyol, alicyclic polyether polyol, aromatic polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, etc. are mentioned.
Examples of the aliphatic polyether polyol include at least one selected from ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, substituted tetrahydrofuran, oxetane, substituted oxetane, tetrahydropyran, and oxeban. Examples thereof include those obtained by ring-opening (co) polymerizing a compound. Specific examples thereof include polyethylene glycol, 1,2-polypropylene glycol, 1,3-polypropylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, polyisobutylene glycol, copolymer polyol of propylene oxide and tetrahydrofuran. Copolymer polyols of ethylene oxide and tetrahydrofuran, copolymer polyols of ethylene oxide and propylene oxide, copolymer polyols of tetrahydrofuran and 3-methyltetrahydrofuran, copolymer polyols of ethylene oxide and 1,2-butylene oxide, etc. Can be mentioned.
Examples of the alicyclic polyether polyol include hydrogenated bisphenol A ethylene oxide addition diol, hydrogenated bisphenol A propylene oxide addition diol, hydrogenated bisphenol A butylene oxide addition diol, and hydrogenated bisphenol F ethylene oxide addition diol. And propylene oxide addition diol of hydrogenated bisphenol F, butylene oxide addition diol of hydrogenated bisphenol F, dimethylol compound of dicyclopentadiene, tricyclodecane dimethanol and the like.

  As commercial products of aliphatic polyether polyol and alicyclic polyether polyol, Unisafe DC1100, Unisafe DC1800, Unisafe DCB1100, Unisafe DCB1800 (above, manufactured by NOF Corporation); PPTG4000, PPTG2000, PPTG1000, PTG2000, PTG3000, PTG650, PTGL2000, PTGL1000 (above, manufactured by Hodogaya Chemical Co., Ltd.); EXENOL4020, EXENOL3020, EXENOL2020, EXENOL1020 (above, manufactured by Asahi Glass Co., Ltd.); 4200, 6300, 8200 (above, Sumika Bayer Urethane Co., Ltd.); NPML-20 2,3002,4002,8002 (above, manufactured by Asahi Glass Co., Ltd.), and the like.

Examples of the aromatic polyether polyol include bisphenol A ethylene oxide addition diol, bisphenol A propylene oxide addition diol, bisphenol A butylene oxide addition diol, bisphenol F ethylene oxide addition diol, bisphenol F propylene oxide addition diol, Examples include butylphenol addition diol of bisphenol F, alkylene oxide addition diol of hydroquinone, alkylene oxide addition diol of naphthoquinone, and the like. Examples of commercially available aromatic polyether polyols include Uniol DA400, DA700, DA1000 (manufactured by NOF Corporation) and the like.
Examples of the polyester polyol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 3-methyl. Polyhydric alcohols such as -1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, Examples include polyester polyols obtained by reacting polybasic acids such as sebacic acid. Examples of commercially available products include Kurapol P-2010, PMIPA, PKA-A, PKA-A2, and PNA-2000 (manufactured by Kuraray Co., Ltd.).

Examples of the polycarbonate polyol include 1,6-hexane polycarbonate. As commercial products, DN-980, 981, 982, 983 (more, manufactured by Nippon Polyurethane Co., Ltd.); PLACEL-CD205, CD-983, CD220 (more, manufactured by Daicel Chemical Industries); PC-8000 (produced by PPG, USA) Etc.
As polycaprolactone polyol, ε-caprolactone, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol Polycaprolactone diol obtained by reacting with diols such as 1,4-cyclohexanedimethanol and 1,4-butanediol. As a commercial item, PLACC CEL205,205AL, 212,212AL, 220,220AL (above, Daicel Chemical Industries Ltd. make) etc. are mentioned.
Other polyol compounds that can be used in the present invention include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedi Examples include methanol, poly β-methyl-δ-valerolactone, hydroxy-terminated polybutadiene, hydroxy-terminated hydrogenated polybutadiene, castor oil-modified polyol, polydimethylsiloxane-terminated diol compound, and polydimethylsiloxane carbitol-modified polyol.
Of the polyol compounds, polyether polyols are preferable, and aliphatic polyether polyols having an alkyleneoxy structure are more preferable. Specifically, polypropylene glycol, ethylene oxide / propylene oxide copolymer diol, ethylene oxide / 1,2-butylene oxide copolymer diol, and propylene oxide / tetrahydrofuran copolymer diol are more preferable, and ethylene oxide / 1,2-butylene oxide. A copolymerized diol is particularly preferred.
(A) A polyol compound may be used independently or may use 2 or more types together.

  (A) The number average molecular weight of the polyol compound is preferably 500 to 10,000, more preferably 1,000 to 8,000, and most preferably 1,500 to 5,000. (A) When the number average molecular weight of the polyol compound is less than 500, the Young's modulus at room temperature and low temperature of the antistatic layer obtained by curing the composition is increased, and a film-like optical waveguide having sufficient bending durability is obtained. Can't get. On the other hand, when the number average molecular weight exceeds 10,000, the viscosity of the composition increases, and the applicability may deteriorate.

[(B) Polyisocyanate compound]
(B) Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethylphenylene diisocyanate, 4,4′-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate 1,4-hexamethylene diisocyanate, bis (2-isocyanate ethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl And polyisocyanate compounds such as xylylene diisocyanate. Of these, hydrogenated xylylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and the like are preferable.
(B) A polyisocyanate compound may be used independently or may use 2 or more types together.

[(C) Hydroxyl group-containing (meth) acrylate]
(C) Examples of the hydroxyl group-containing (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenyloxy. Propyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neo Pentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol pen (Meth) acrylate. Furthermore, the compound obtained by addition reaction of glycidyl group containing compounds, such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid is mentioned. Of these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like are preferably used.
(C) The hydroxyl group-containing (meth) acrylate may be used alone or in combination of two or more.
The blending ratio of the respective raw materials constituting the component (A) is, for example, (c) 0.5 to 2 mol of a polyol compound and (b) a polyisocyanate compound with respect to 1 mol of a hydroxyl group-containing (meth) acrylate. 1 to 2.5 moles.

As a component (A), a urethane (meth) acrylate oligomer may be used individually by 1 type, or 2 or more types may be used together.
The number average molecular weight of the component (A) is preferably 100 to 15,000, more preferably 300 to 12,000. If the value is less than 100, the viscosity of the composition becomes too small, and the coatability may be inferior. On the other hand, when the value exceeds 15,000, the viscosity becomes high and handling becomes difficult.
The amount of component (A) in the optical waveguide coating composition is preferably 30 to 80 parts by mass, more preferably 35 to 75 parts by mass, with the total amount of components (A) to (E) being 100 parts by mass. Part, particularly preferably 40 to 70 parts by weight. When the blending amount is less than 30 parts by mass, the Young's modulus of the antistatic layer obtained by curing the composition is increased, and it becomes difficult to maintain sufficient bending durability of the film-shaped optical waveguide. On the other hand, when the blending amount exceeds 80 parts by mass, the viscosity of the composition increases, and it becomes difficult to form an antistatic layer having a uniform thickness.

[Component (B)]
Component (B) is a monomer having one or more (meth) acryloyl groups in the molecule.
Examples of component (B) include (B1) a compound having one (meth) acryloyl group in the molecule, and (B2) a compound having two or more (meth) acryloyl groups in the molecule.
Examples of (B1) (compound having one (meth) acryloyl group in the molecule) include acryloylmorpholine, dimethylacrylamide, diethylacrylamide, diisopropylacrylamide, isobornyl (meth) acrylate, dicyclopentenyl acrylate, Cyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl methacrylate, dicyclopentadienyl (meth) acrylate, tricyclodecanyl (meth) Acrylate, diacetone acrylamide, isobutoxymethyl (meth) acrylamide, 3-hydroxycyclohexyl acrylate, 2-acryloylcyclohexyl succinic acid, Mention may be made of the E Roh carboxyethyl acrylate, and the like.
Among these, isobornyl (meth) acrylate is preferably used because it is excellent in heat resistance and significantly improves the long-term reliability of the film-like optical waveguide.
As commercial products of the component (B1), ACMO, DMAA (manufactured by Kojin Co., Ltd.), New Frontier IBA (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); IBXA (manufactured by Osaka Organic Chemical Co.); FA511A, FA512A, FA513A (and above, Hitachi Chemical Co., Ltd.); Light Ester M, E, BH, TB, IB-X, IB-XA (above, Kyoeisha Chemical Co., Ltd.); Aronix M150, M156, TO1315, TO1316 (above, Toagosei Co., Ltd.); FA544A 512M, 512MT, 513M (Hitachi Chemical Co., Ltd.) and the like.

Examples of (B2) (compound having two or more (meth) acryloyl groups in the molecule) include, for example, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, brominated epoxy acrylate, bis (hydroxymethyl) tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-added bisphenol A di (meta) ) Acrylate, ethylene oxide-added tetrabromobisphenol A type di (meth) acrylate, propylene oxide added bisphenol A type di (meth) acrylate, propylene oxide added tetrabromobisphenol A type di (meth) acrylate, bisphenol A diglycidyl ether and ( Bisphenol A type epoxy di (meth) acrylate obtained by epoxy ring-opening reaction with (meth) acrylic acid, tetrabromobisphenol A diglycy Bisphenol F type obtained by epoxy ring-opening reaction of tetrabromobisphenol A type epoxy di (meth) acrylate, bisphenol F diglycidyl ether and (meth) acrylic acid obtained by epoxy ring-opening reaction of ruether and (meth) acrylic acid Examples thereof include epoxy di (meth) acrylate, tetrabromobisphenol F-type epoxy di (meth) acrylate obtained by an epoxy ring-opening reaction between tetrabromobisphenol F diglycidyl ether and (meth) acrylic acid.
Among them, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, ethylene oxide-added bisphenol A type di (meth) acrylate, ethylene oxide added tetrabromobisphenol A type di (meth) acrylate, bisphenol A di Bisphenol A type epoxy di (meth) acrylate, tetrabromobisphenol A type epoxy di (meth) acrylate, and the like obtained by epoxy ring-opening reaction between glycidyl ether and (meth) acrylic acid are particularly preferably used.

  As a commercial item of a component (B), for example, Biscote # 700, # 540 (above, Osaka Organic Chemical Industry Co., Ltd.); Aronix M-208, M-210 (above, Toagosei Co., Ltd.); NK ester BPE- 100, BPE-200, BPE-500, A-BPE-4, A-BPEF (manufactured by Shin-Nakamura Chemical Co., Ltd.); light acrylate 1,6-HX-A, light ester BP-4EA, BP-4PA, epoxy Esters 3002M, 3002A, 3000M, 3000A (above, manufactured by Kyoeisha Chemical Co., Ltd.); KAYARAD R-551, R-712 (above, manufactured by Nippon Kayaku Co., Ltd.); BPE-4, BPE-10, BR-42M (above, No. 1) Manufactured by Ichi Kogyo Seiyaku Co., Ltd.); Lipoxy VR-77, VR-60, VR-90, SP-1506, SP-1506, SP-1507, SP-150 , SP-1563 (manufactured by Showa High Polymer Co., Ltd.); NEOPOL V779, NEOPOL V779MA (manufactured by Japan U-PICA Co., Ltd.), and the like.

As the component (B), it is preferable to use the component (B1) and the component (B2) in combination. That is, the component (B) preferably includes at least one (B1) component and at least one (B2) component. The blending ratio (B1 / B2) of the component (B1) and the component (B2) is a mass ratio, preferably 0.2 / 1 to 0.9 / 1, more preferably 0.3 / 1 to 0. .8 / 1.
The amount of component (B) in the optical waveguide coating composition is 15 to 50 parts by mass, preferably 20 to 45 parts by mass, with the total amount of components (A) to (E) being 100 parts by mass. Preferably it is 25-40 mass parts. When the blending amount of component (B) is less than 15 parts by mass, the heat and humidity resistance of the antistatic layer obtained by curing the composition is lowered, and the film-like optical waveguide provided with the antistatic layer is used in a high temperature and high humidity atmosphere. In this case, it becomes difficult to maintain good transmission characteristics and bending durability. On the other hand, when the compounding amount of component (B) exceeds 50 parts by mass, the photocurability of the composition is lowered, and it becomes difficult to form an antistatic layer having sufficient mechanical properties.

[Component (C)]
Component (C) is a photoradical polymerization initiator that can generate an active species (radical) capable of polymerizing component (A) and component (B) by light.
Here, light means ionizing radiation such as infrared rays, visible rays, ultraviolet rays, and X-rays, electron beams, α rays, β rays, and γ rays.
Examples of the photo radical polymerization initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3 -Methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2- Hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthio Sandone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, And bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide. Among these, 1-hydroxycyclohexyl phenyl ketone and the like are preferably used from the viewpoints of polymerization rate and solution stability.

Examples of commercially available components (C) include Irgacure 184, 369, 379, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1116, 1173 (or above). Ciba Specialty Chemicals); Lucirin TPO, LR8883, LR8970 (above, manufactured by BASF); Ubekrill P36 (UCB), and the like. A radical photopolymerization initiator is used individually by 1 type or in combination of 2 or more types.
In the present invention, a photosensitizer can be used together with a photopolymerization initiator. Examples of the photosensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. Isoamyl etc. are mentioned. Examples of commercially available photosensitizers include Ubekryl P102, 103, 104, and 105 (above, manufactured by UCB).

  In the optical waveguide coating composition, the amount of component (C) is 0.1 to 10 parts by weight, preferably 0.3 to 7 parts by weight, with the total amount of components (A) to (E) being 100 parts by weight. Part, more preferably 0.5 to 5 parts by mass. When the blending amount is less than 0.1 parts by mass, curing does not proceed sufficiently, and it may be difficult to form an antistatic layer having sufficient mechanical properties. Moreover, when this compounding quantity exceeds 10 mass parts, a photoinitiator may have a bad influence on the long-term characteristic of an antistatic layer.

[Component (D)]
Component (D) is an antistatic agent. As the antistatic agent used as the component (D), various materials known as antistatic agents for polymer materials can be used.
Examples of the antistatic agent used as the component (D) include lithium perfluoroethanoate, lithium perfluoropropanoate, lithium perfluorobutanoate, lithium perfluoropentanoate, lithium perfluorohexanoate, and lithium perfluoroheptanoate. , Lithium perfluorooctanoate, lithium perfluorononanoate, lithium perfluorodecanoate, lithium trifluoromethanesulfonate, lithium perfluoroethanesulfonate, lithium perfluoropropanesulfonate, lithium perfluorobutanesulfonate, perfluoropentanesulfone Lithium acid, lithium perfluorohexanesulfonate, lithium perfluoroheptanesulfonate, lithium perfluorooctanesulfonate, perfluorononane Lithium sulfonate, lithium bistrifluoromethanesulfonylimide, lithium bisperfluoroethanesulfonylimide, lithium bisperfluoroethanesulfonylimide, lithium bisperfluoropropanesulfonylimide, lithium bisperfluorobutanesulfonylimide, lithium bisperfluoropentanesulfonylimide , Lithium bisperfluorohexanesulfonylimide, lithium bisperfluoroheptanesulfonylimide, lithium bisperfluorooctanesulfonylimide, lithium bisperfluorononanesulfonylimide, lithium bistrifluoromethanecarboimide, lithium bisperfluoroethaneimide, lithium bis Perfluoropropanoic acid imide, lithium bisperfluorobutane Imido, lithium bisperfluoropentanoic acid imide, lithium bisperfluorohexanoic acid imide, lithium bisperfluoroheptanoic acid imide, lithium bisperfluorooctanoic acid imide, lithium bisperfluorononanoic acid imide, lithium bisperfluorodecanoic acid imide, etc. Lithium salt-based antistatic agents; aromatic ions having pyridinium ions, imidazolium ions, etc. as cations, aliphatic amine ions having trimethylhexylammonium ions, etc., and NO ₃ ⁻ , as anions, ^{_{CH 3 CO 2 -, BF 6}} -, PF 6 - or the like inorganic ^{_{ionic, (CF 3 SO 2) 2}} N -, CF 3 CO 2 -, CF 3 SO 2 - have the like fluorine-containing organic anions, etc. Ionic liquid antistatic agent; quaternary ammonium A salt-based antistatic agent is preferably used.

  As a commercial item of component (D), for example, a mixture of a lithium salt antistatic agent and a compound having a polymerizable unsaturated group, Sanconol A600-50R, Sanconol A600-30R, A600-20R, PETA-30R , PETA-20R, A400-20R, MEK-50R (manufactured by Sanko Chemical Industry Co., Ltd.); IL-P14 and IL-A2 (manufactured by Guangei Chemical Industry Co., Ltd.) which are ionic liquid antistatic agents; Examples thereof include Elegan 264-WAX and SS-100 (manufactured by NOF Corporation), which are salt-based antistatic agents. An antistatic agent is used individually by 1 type or in combination of 2 or more types.

  In the optical waveguide coating composition, the amount of component (D) is 0.3 to 15 parts by mass, preferably 0.6 to 10 with 100 parts by mass as the total amount of components (A) to (E). Part by mass, particularly preferably 1 to 5 parts by mass. When the blending amount is less than 0.3 parts by mass, the antistatic property is lowered. On the other hand, when the blending amount exceeds 15 parts by mass, the bending durability of the film-shaped optical waveguide provided with the antistatic layer obtained by curing the coating composition for optical waveguide may be adversely affected.

（式中、Ｒ^１、Ｒ^３及びＲ^４は各々独立して水素原子またはメチル基であり、Ｒ^２はラジカル重合性反応基を含む有機基であり、Ｘ及びＺは各々独立して単結合または２価の有機基であり、Ｙは重合性を有しない有機基を示す。） [Component (E)]
The optical waveguide coating composition may further contain a polymer having a radical polymerizable reactive group other than the component (A) as the component (E). By mix | blending a component (E), moderate viscosity may be provided and coating property may become favorable.
For example, the component (E) includes a structure represented by the following general formulas (1) to (3), and the ratio of the structure represented by the following general formula (1) is 5 to 40 mol%. The polymer whose ratio of the structure represented by Formula (2) is 30-90 mol% and the ratio of the structure represented by following General formula (3) is 5-30 mol% can be used.

(Wherein R ¹ , R ³ and R ⁴ are each independently a hydrogen atom or a methyl group, R ² is an organic group containing a radically polymerizable reactive group, and X and Z are each independently a single bond) Or, it is a divalent organic group, and Y represents an organic group having no polymerizability.)

（式中、Ｒ^１は水素原子または炭素数１〜１２のアルキル基であり、Ｒ^５は水素原子またはメチル基であり、Ｘ及びＺは各々独立して、単結合または２価の有機基を示す。） Preferable examples of the repeating unit represented by the general formula (1) include a repeating unit represented by the following general formula (4).

(Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ⁵ is a hydrogen atom or a methyl group, and X and Z are each independently a single bond or a divalent organic group. Show.)

（式中、Ｒ^６は、メチレンまたは炭素数２〜８のアルキレン基である。）
一般式（２）において、Ｙの例としては、下記一般式（６）で表される構造を有する有機基や、フェニル基や、環状アミド基、ピリジル基等が挙げられる。

（式中、Ｒ^７は、炭素数１〜２０の直鎖状、分岐状または環状の炭素を有する基である。）
一般式（３）において、Ｚ（２価の有機基）の例としては、メチレンまたは炭素数２〜８のアルキレン基等が挙げられる。 In the general formula (1), examples of the radical polymerizable reactive group in R ² include a vinyl group, an allyl group, and a (meth) acryloyl group.
In the general formulas (1) and (4), examples of X include an organic group having a structure represented by the following general formula (5), a phenylene group, and the like.

(In the formula, R ⁶ is methylene or an alkylene group having 2 to 8 carbon atoms.)
In the general formula (2), examples of Y include an organic group having a structure represented by the following general formula (6), a phenyl group, a cyclic amide group, and a pyridyl group.

(Wherein R ⁷ is a group having a linear, branched or cyclic carbon having 1 to 20 carbon atoms.)
In the general formula (3), examples of Z (divalent organic group) include methylene or an alkylene group having 2 to 8 carbon atoms.

  The amount of component (E) is 0 to 40 parts by weight, preferably 0 to 35 parts by weight, more preferably 0 to 30 parts by weight, with the total amount of components (A) to (E) being 100 parts by weight. is there. When the blending amount exceeds 40 parts by mass, the viscosity of the composition increases, it becomes difficult to form an antistatic layer having a uniform thickness, or the blending ratio of component (A) decreases. The bending durability of the antistatic layer may be reduced.

Examples of the method for producing component (E) include radical polymerization of (a) a radical polymerizable compound having a hydroxyl group and (b) component (radical polymerizable compound corresponding to general formula (2)) in a solvent. Then, the method of adding the isocyanate which has (c) (meth) acryloyl group with respect to the hydroxyl group of the side chain of the obtained copolymer is mentioned.
The compounds (a) to (c) used in this method will be described.

The compound (a) (radical polymerizable compound having a hydroxyl group) reacts with a hydroxyl group in the compound and an isocyanate group (—N═C═O) in the compound (c) to form a urethane bond (—NH—COO). -) And a structural unit having a side chain portion containing a (meth) acryloyl group derived from the compound (c) is used to introduce into the component (E).
Examples of the compound (a) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxymethyl (meth) acrylate, and 4-hydroxycyclohexyl (meth). An acrylate etc. are mentioned.
The content of the compound (a) in the component (E) is preferably 3 to 80% by mass, more preferably 5 to 60% by mass, and particularly preferably 10 to 40% by mass.
When the content is less than 3% by mass, curing tends to be insufficient. When this content rate exceeds 80 mass%, the optical characteristic (refractive index) of a film-form optical waveguide may fall.

The compound (b) (compound corresponding to the structure of the general formula (2)) is mainly used for moderately controlling the mechanical properties of the component (E).
Examples of the compound (b) include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and t-butyl (meth) acrylate. (Meth) acrylic acid alkyl esters such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclo [5.2.1.2.6] decan-8-yl methacrylate and the like ( Esters of (meth) acrylic acid and cyclic hydrocarbon compounds; (meth) such as phenyl (meth) acrylate, benzyl (meth) acrylate, o-phenylphenol glycidyl ether (meth) acrylate, p-cumylphenoxyethylene glycol acrylate Aryl acrylate ester Tribromophenol ethoxy (meth) acrylate, 2,2,2-trifluoromethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl Halogenated (meth) acrylic esters such as (meth) acrylate and perfluorooctylethyl (meth) acrylate; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, etc. Aromatic vinyls; conjugated diolefins such as 1,3-butadiene, isoprene and 1,4-dimethylbutadiene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; amide bonds such as acrylamide and methacrylamide Polymerizable compound; vinyl acetate And fatty acid vinyls such as
Among them, methyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, tricyclo [5.2.1.2.6.6] decane-8- Il = methacrylate, styrene, α-methylstyrene and the like are preferably used.
A compound (b) is used individually by 1 type or in combination of 2 or more types.
The content of the compound (b) in the component (E) is preferably 15 to 95% by mass, more preferably 25 to 90% by mass, and particularly preferably 35 to 85% by mass.
When the content is less than 15% by mass, the optical properties (refractive index) of the film-shaped optical waveguide may be lowered. If the content exceeds 92% by mass, curing tends to be insufficient.

Examples of the compound (c) (isocyanate having a (meth) acryloyl group) include 2-methacryloyloxyethyl isocyanate, N-methacryloyl isocyanate, methacryloyloxymethyl isocyanate, methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, N- Examples include acryloyl isocyanate, acryloyloxymethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, 1,1-bis (methacryloyloxymethyl) ethyl isocyanate.
The content of the compound (c) in the component (E) is preferably 2 to 80% by mass, more preferably 5 to 60% by mass, and particularly preferably 5 to 45% by mass.
When the content is less than 5% by mass, curing tends to be insufficient. When this content rate exceeds 80 mass%, the optical characteristic (refractive index) of a film-form optical waveguide may fall.

Component (E) can also contain structural units other than the structural units represented by general formulas (1) to (3). Examples of the compound for introducing such a structural unit (hereinafter referred to as compound (d)) include dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate; vinyl chloride, vinylidene chloride, etc. And a chlorine-containing polymerizable compound. The content rate of the compound (d) in a component (E) becomes like this. Preferably it is 0-20 mass%, More preferably, it is 0-10 mass%.
In the production process of the component (E), various additives such as a thermal polymerization inhibitor, a storage stabilizer, and a curing catalyst can be added during the addition reaction of the compound (c).
The thermal polymerization inhibitor is blended in order to suppress a polymerization reaction due to heat. Examples of thermal polymerization inhibitors include pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methoxyphenol, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether and the like.
Examples of the storage stabilizer include 2,6-di-t-butyl-p-cresol, benzoquinone, p-toluquinone, p-xyloquinone, phenyl-α-naphthylamine and the like.
Examples of the curing catalyst include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioleate, dibutyltin diacetate, tetramethoxytitanium, tetraethoxytitanium and the like.
The total compounding amount of these various additives is usually 10 parts by mass or less, preferably 5 parts by mass or less with respect to 100 parts by mass of the total amount of the compounds (a) to (d).

Examples of the solvent that can be used for radical polymerization of the compound (a), the compound (b), and the compound (d) used as necessary in the production of the component (E) include methanol, ethanol, ethylene glycol, and diethylene glycol. , Alcohols such as propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomer Alkyl ethers of polyhydric alcohols such as ether and propylene glycol monoethyl ether; alkyl ether acetates of polyhydric alcohols such as ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol monomethyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, diacetone alcohol; ethyl acetate, butyl acetate, ethyl lactate, Ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropio Ethyl acetate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc. Examples include esters.
Of these, cyclic ethers, polyhydric alcohol alkyl ethers, polyhydric alcohol alkyl ether acetates, ketones, and esters are preferred.

On the other hand, when a solvent having a hydroxyl group in the molecule is used as the solvent used in the addition reaction of compound (c) in the production of component (E), compound (c) reacts with the solvent, which is not preferable. . Therefore, the solvent used for the addition reaction of compound (c) is preferably one having no hydroxyl group. Examples of the solvent having no hydroxyl group include those having no hydroxyl group among the solvents used for the radical polymerization.
Moreover, as a catalyst for radical polymerization used for manufacture of a component (E), a normal radical polymerization initiator can be used. Examples of radical polymerization initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2, Azo compounds such as 4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis (t-butylperoxy) cyclohexane; and hydrogen peroxide Can be mentioned. When a peroxide is used as the radical polymerization initiator, a redox initiator may be used in combination with a reducing agent.

  It is preferable that the glass transition temperature of a component (E) is 20 to 150 degreeC. At this time, the glass transition temperature is defined as a value obtained by measurement using a differential scanning calorimeter (DSC) which is usually performed. When the temperature is less than 20 ° C., it becomes difficult to form an antistatic layer formed by curing the coating composition for optical waveguides, or stickiness occurs in the layers, and a film-shaped optical waveguide is laminated. There are inconveniences such as poor workability. Conversely, when the temperature exceeds 150 ° C., the antistatic layer becomes hard or brittle, and the bending durability of the film-shaped optical waveguide may be lowered.

[Component (F)]
It is preferable that an organic solvent is further blended in the optical waveguide coating composition as the component (F). By blending the organic solvent, the storage stability of the optical waveguide coating composition is improved, and an appropriate viscosity can be imparted to form a layer having a uniform thickness.
The type of the organic solvent can be appropriately selected within a range that does not impair the object and effect of the present invention, but has a boiling point within the range of 50 to 200 ° C. under atmospheric pressure, and each constituent component Those that dissolve uniformly are preferred.
Preferable examples of the organic solvent include alcohols, ethers, esters, and ketones. Preferable compound names of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethylene glycol dimethyl ether, methyl isobutyl ketone, methyl amyl ketone, toluene, xylene, methanol and the like.
An organic solvent may be used individually by 1 type, and may use 2 or more types together.
The compounding amount of the organic solvent is preferably 0 to 200 parts by mass, more preferably 0 to 150 parts by mass, and particularly preferably 0 to 100 parts by mass with respect to 100 parts by mass of the total amount of the components (A) to (E). Part. When the amount exceeds 200 parts by mass, it may be difficult to form an antistatic layer having a sufficient thickness.
In addition, adjustment of the viscosity of the coating composition for optical waveguides can be easily performed by using an organic solvent.

In the coating composition for optical waveguides of the present invention, in addition to the above components (A) to (F), as long as the properties of the resin composition of the present invention are not impaired as necessary, for example, the component (A), Compounds having polymerizable reactive groups other than component (B) and component (E), and polymer resins (for example, epoxy resins, acrylic resins, polyamide resins, polyamideimide resins, polyurethane resins, polybutadiene resins, polychloroprene resins, poly An ether resin, a polyester resin, a styrene-butadiene block copolymer, a petroleum resin, a xylene resin, a ketone resin, a cellulose resin, a fluorine-based polymer, a silicone-based polymer) and the like can be blended.
Furthermore, various additives as necessary, for example, antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, coating surface improvers, thermal polymerization inhibitors, leveling agents, surfactants, colorants, Storage stabilizers, plasticizers, lubricants, fillers, inorganic particles, anti-aging agents, wettability improvers, and the like can be blended.
In order to prepare a coating composition for an optical waveguide, the above-mentioned components may be mixed and stirred according to a conventional method.

  As a material for forming the optical waveguide (lower clad layer, core portion, upper clad layer) of the film-shaped optical waveguide of the present invention, for example, acrylic is used from the viewpoint of adhesion between the film-shaped optical waveguide and the antistatic layer. A photocurable resin composition of the type is preferably used. When a film-shaped optical waveguide is formed using an acrylic photocurable resin composition, good adhesion can be obtained without performing surface treatment on the contact surface with the antistatic layer. Examples of the acrylic photo-curable resin composition include OPSTAR PJ3074 and OPSTAR PJ3075 (trade name; manufactured by JSR Corporation).

[Method for producing film-shaped optical waveguide]
FIG. 2 is a flowchart showing an example of the method for producing a film-shaped optical waveguide of the present invention. The manufacturing method of the film-like optical waveguide 24 of the present invention includes the step of forming the antistatic layer 8, the step of forming the lower cladding layer 10, the step of forming the core portion 18, and the step of forming the upper cladding layer 20. And a step of forming the antistatic layer 22. Of these steps, the step of forming the antistatic layer 8 and the step of forming the antistatic layer 22 are steps of curing the optical waveguide coating composition by light irradiation.
The optical waveguide coating composition for forming the antistatic layer 8 and the optical waveguide coating composition for forming the antistatic layer 22 are referred to as a lower protective layer composition and an upper protective layer composition, respectively, for convenience. . Moreover, the photocurable resin composition for forming each part of the lower clad layer 10, the core part 18 and the upper clad layer 20 constituting the film-shaped optical waveguide is respectively a lower layer composition and a core composition for convenience. And an upper layer composition.
(1) Preparation of photocurable resin composition When forming the antistatic layers 8 and 22 on both surfaces of the film-like optical waveguide 24, each component composition of the lower protective layer composition and the upper protective layer composition is: Although it is not particularly limited, the same coating composition for an optical waveguide is preferable in terms of economy and production management.
The viscosity of the coating composition for an optical waveguide for forming an antistatic layer is preferably 1 to 10,000 cps (25 ° C.), more preferably 5 to 8,000 cps (25 ° C.), and particularly preferably 10 to 5,000 cps ( 25 ° C.). When the viscosity is outside this range, it may be difficult to handle the coating composition for optical waveguides or to form a uniform coating film. In addition, a viscosity can be suitably adjusted by changing compounding quantities, such as an organic solvent.
On the other hand, each component composition of the lower layer composition, the core composition, and the upper layer composition requires the optical waveguide to have a refractive index relationship between the lower cladding layer 10, the core portion 18 and the upper cladding layer 20. It is determined to satisfy the following conditions. Specifically, two or three kinds of photocurable resin compositions having a suitable difference in refractive index are prepared, and among these, a photocurable resin composition that gives a cured film having the highest refractive index. Is used as a core composition, and other photocurable resin compositions are used as a lower layer composition and an upper layer composition.
The lower layer composition and the upper layer composition are preferably the same photocurable resin composition in terms of economy and production control.

(2) Preparation of Substrate As shown in FIG. 2A, a substrate 2 having a flat surface is prepared. Although it does not specifically limit as a kind of this board | substrate 2, For example, a silicon substrate, a glass substrate, etc. can be used.
(3) First Antistatic Layer Forming Step In this step, the antistatic layer 8 is formed on the upper surface of the substrate 2. Specifically, as shown in FIG. 2B, the lower protective layer composition is applied to the surface of the substrate 2 and dried or prebaked to form the protective layer thin film 4. The protective layer thin film 4 is irradiated with light 6 and cured to form an antistatic layer 8 which is a cured body (see (c) and (d) in FIG. 2). In addition, in the formation process of the antistatic layer 8, it is preferable to irradiate the whole surface of a thin film and to harden the whole.
Coating methods for the protective layer composition (optical waveguide coating composition) include spin coating, dipping, spraying, bar coating, roll coating, curtain coating, gravure printing, silk screen, and inkjet. Any method such as a method can be used. Among these, since the thin film for protective layers of uniform thickness is obtained, it is preferable to employ | adopt a spin coat method.
Moreover, it is preferable to pre-bake the thin film for protective layers which consists of a composition for protective layers at the temperature of 50-200 degreeC for the purpose of removing an organic solvent etc. after application | coating.

The irradiation amount of light when forming the antistatic layer 8 is not particularly limited, but light having a wavelength of 200 to 450 nm and an illuminance of 1 to 500 mW / cm ² is irradiated with an irradiation amount of 10 to 5,000 mJ / cm. It is preferable to perform exposure by irradiating so as to be ² .
Visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays, and the like can be used as the type of light to be irradiated, and ultraviolet rays are particularly preferable. As the light irradiation device, for example, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, an excimer lamp, or the like is preferably used.
Further, after the exposure, a heat treatment (post-bake) can be further performed. This heating condition varies depending on the component composition of the composition for antistatic layer (coating composition for optical waveguide) and the like, but is usually 30 to 400 ° C, preferably 50 to 300 ° C, more preferably 100 to 200 ° C, For example, the heating time may be 5 minutes to 72 hours. By performing the heat treatment (post-bake), the entire surface of the coating film can be sufficiently cured.
In addition, the coating method of the composition, the light irradiation amount and type, the light (ultraviolet) irradiation device, the pre-bake and post-bake conditions, etc. in the formation process of the antistatic layer 8 are described below. The same applies to.

(4) Formation process of lower clad layer In this process, the lower clad layer 10 is formed on the upper surface of the antistatic layer 8. Specifically, as shown in FIG. 2 (e), a lower layer composition is applied to the upper surface of the antistatic layer 8, and dried or prebaked to form a lower layer thin film. The lower layer thin film is irradiated with light and cured to form a lower cladding layer 10 that is a cured body. In the step of forming the lower cladding layer 10, it is preferable to irradiate the entire surface of the thin film with light and harden the whole.
Here, as a coating method of the composition for the lower layer, any of spin coating method, dipping method, spray method, bar coating method, roll coating method, curtain coating method, gravure printing method, silk screen method, ink jet method, etc. The method can be used. Among these, since a thin film for a lower layer having a uniform thickness can be obtained, it is preferable to employ a spin coating method.
In addition, in order to make the rheological properties of the lower layer composition suitable for the coating method, the lower layer composition requires various leveling agents, thixotropic agents, fillers, organic solvents, surfactants, etc. It is preferable to mix according to this.
Moreover, it is preferable to pre-bake the thin film for lower layers which consists of a composition for lower layers at the temperature of 50-200 degreeC for the purpose of removing an organic solvent etc. after application | coating.
The coating method in the lower clad layer forming step, improvement of rheological characteristics, and the like are the same in the core step forming step and the upper clad layer forming step, which will be described later.

The amount of light irradiation when forming the lower clad layer is not particularly limited, but light having a wavelength of 200 to 450 nm and an illuminance of 1 to 500 mW / cm ² is irradiated in an amount of 10 to 5,000 mJ / cm ^2. It is preferable that the exposure is performed by irradiation.
Visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays, and the like can be used as the type of light to be irradiated, and ultraviolet rays are particularly preferable. As the light irradiation device, for example, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, an excimer lamp, or the like is preferably used.
Moreover, it is preferable to perform a heat treatment (post-bake) after the exposure. Although this heating condition changes with component composition etc. of a photocurable resin composition, it is 30-400 degreeC normally, Preferably it is 50-300 degreeC, More preferably, it is 100-200 degreeC, for example, for 5 minutes-72 hours heating. Time can be taken. By performing the heat treatment (post-bake), the entire surface of the coating film can be sufficiently cured.
The light irradiation amount, type, and light (ultraviolet) irradiation device in the lower clad layer forming step are the same in the core portion forming step and the upper clad layer forming step, which will be described later.

(5) Core Part Formation Step Next, as shown in FIG. 2 (f), the core composition is applied to the upper surface of the lower cladding layer 10 and dried or prebaked to form the core thin film 12. To do. Thereafter, as shown in FIG. 2G, irradiation (exposure) of light 16 is performed on the upper surface of the core thin film 12 according to a predetermined pattern, for example, through a photomask 14 having a predetermined line pattern. Do. As a result, only the portion irradiated with light in the core thin film 12 is cured, so that other uncured portions are developed and removed, as shown in FIG. On the lower clad layer 10, a core portion 18 made of a patterned cured film can be formed.
The details of the development processing in this step are as follows.
The development process is carried out in accordance with a predetermined pattern, and for the thin film selectively cured, using the difference in solubility between the cured portion and the uncured portion, only the uncured portion is developed using a developer. The removal is performed. That is, after pattern exposure, the uncured portion is removed and the cured portion is left, resulting in the formation of the core portion.

An organic solvent can be used as the developer used in the development process. Examples of the organic solvent include acetone, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol monomethyl ether acetate, methyl amyl ketone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, and the like.
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. After the development, the organic solvent is removed by air drying as it is, and a patterned thin film is formed.
After the formation of the patterned thin film (patterning portion), the patterning portion is heat-treated (post-baked). Although this heating condition changes with component composition of a photocurable resin composition, etc., it is 30-400 degreeC normally, Preferably it is 50-300 degreeC, More preferably, it is 100-200 degreeC, for example, for 5 minutes-10 minutes. What is necessary is just to set it as the heating time of time. By performing the heat treatment (post-bake), the entire surface of the coating film can be sufficiently cured.

In this step, the method of irradiating light according to a predetermined pattern is not limited to the method using the photomask 14 composed of the light transmitting portion and the non-transmitting portion, and for example, any of the following methods a to c May be adopted.
a. A method using electro-optical means for forming a mask image composed of a light transmitting region and a light non-transmitting region in accordance with 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 photocurable resin composition while scanning a laser beam or convergent light obtained by a condensing optical system such as a lens or a mirror.

(6) Formation process of upper clad layer The upper layer composition is applied to the upper surfaces of the core portion 18 and the lower clad layer 10, and dried or prebaked to form an upper layer thin film. When this upper thin film is cured by irradiation with light, an upper clad layer 20 is formed as shown in (i) of FIG.
Further, the entire surface of the coating film can be sufficiently cured by subjecting the upper clad layer 20 to heat treatment (post-baking). This heating condition is usually 30 to 400 ° C., preferably 50 to 300 ° C., more preferably 100 to 200 ° C., for example, a heating time of 5 minutes to 72 hours.

(7) Second Antistatic Layer Forming Step In this step, the antistatic layer 22 is formed on the upper surface of the upper clad layer 20. Specifically, as shown in FIG. 2 (j), the upper protective layer composition is applied to the upper surface of the upper clad layer, and dried or prebaked to form a protective layer thin film. The antistatic layer 22 that is a cured body is formed by irradiating the thin film with light and curing it. In addition, in the formation process of the antistatic layer 22, it is preferable to irradiate the whole surface of a thin film and to harden the whole. After the exposure, a heat treatment (post-bake) may be further performed.
As described above, the method for applying the protective layer composition, the pre-bake conditions, the light irradiation amount and type, the light irradiation device, the post-bake conditions, and the like when forming the antistatic layer 22 are as described above. This is the same as the step of forming the protective layer 8.

(8) Peeling of the substrate When the cured product produced in the above steps (1) to (7) is peeled from the substrate 2, a film-like optical waveguide is obtained (see (k) in FIG. 2).
Examples of the peeling method include a method of immersing an optical waveguide produced on a silicon substrate in warm water or hydrofluoric acid.

Hereinafter, the present invention will be specifically described by way of examples.
[1. Preparation of optical waveguide coating composition for antistatic layer]
The following materials were prepared as components (A) to (F).
[Component (A-1)]
In a reaction vessel equipped with a stirrer, 13.6 parts by mass of isophorone diisocyanate, 81.7 parts by mass of polypropylene glycol having a number average molecular weight of 2,000, 0.01 parts by mass of 2,6-di-t-butyl-p-cresol Was cooled to 5 to 10 ° C. While stirring, 0.05 parts by mass of di-n-butyltin dilaurate was added and the mixture was stirred for 2 hours while adjusting the temperature to be kept at 30 ° C. or lower, and then the temperature was raised to 50 ° C. and further stirred for 2 hours. . Subsequently, 4.7 parts by mass of 2-hydroxyethyl acrylate (100 parts by mass in total) was added dropwise, and after the completion of the addition, the reaction was performed at 50 to 70 ° C. for 1 hour. The reaction was terminated when the amount of residual isocyanate was 0.1% by mass or less to obtain Compound A-1.

[Component (A-2)]
In a reaction vessel equipped with a stirrer, 35.4 parts by mass of 2,4-toluene diisocyanate, 41.0 parts by mass of polyoxyethylene bisphenol A ether, 0.01 parts by mass of 2,6-di-t-butyl-p-cresol Was cooled to 5 to 10 ° C. While stirring, 0.05 parts by mass of di-n-butyltin dilaurate was added and the mixture was stirred for 2 hours while adjusting the temperature to be kept at 30 ° C. or lower, and then the temperature was raised to 50 ° C. and further stirred for 2 hours. . Subsequently, 23.6 parts by mass of 2-hydroxyethyl acrylate (100 parts by mass in total above) was added dropwise, and after completion of the addition, the reaction was carried out at 50 to 70 ° C. for 1 hour. The reaction was terminated when the amount of residual isocyanate was 0.1% by mass or less to obtain Compound A-2.
The component compositions of Compound A-1 and Compound A-2 are shown in Table 1.

[Component (B)]
Isobornyl acrylate (OBX Organic Chemical Industries, Ltd., IBXA)
9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Shin-Nakamura Chemical Co., Ltd., A-BPEF)
Bisphenol A EO adduct diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Biscoat # 700)

[Component (C)]
Photoradical polymerization initiator (Ciba Specialty Chemicals, trade name “Irgacure 184”)

[Component (D)]
Lithium salt antistatic agent (San-Econ Chemical Co., Ltd., Sanconol A600-50R)
Quaternary ammonium salt antistatic agent (Nippon Yushi Co., Ltd., Elegan 264-WAX)
Ionic liquid antistatic agent (manufactured by Guangei Chemical Industry Co., Ltd., IL-A2)

[Component (E)]
Preparation Example A flask equipped with a dry ice / methanol reflux was purged with nitrogen, and then charged with 1.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and 90 g of methyl isobutyl ketone as an organic solvent. The mixture was stirred until the polymerization initiator was dissolved. Subsequently, 20 g of 2-hydroxyethyl methacrylate, 25 g of styrene, 35 g of butyl acrylate, 10 g of tricyclo [5.2.1.2.6] decan-8-yl methacrylate and 10 g of methacrylic acid were charged. Gently started stirring. Thereafter, the temperature of the solution was raised to 70 ° C., and polymerization was carried out at this temperature for 6 hours. Thereafter, 0.12 g of di-n-butyltin dilaurate and 0.05 g of 2,6-di-t-butyl-p-cresol were added to the obtained solution, and 11 g of methacryloyloxyethyl isocyanate was added at a temperature of 60. The solution was added dropwise so that the temperature was kept at or below. After completion of the dropwise addition, the mixture was reacted at 60 ° C. for 5 hours to obtain a polymer solution having a methacryl group in the side chain. Thereafter, the reaction product was dropped into a large amount of hexane to solidify the reaction product. Further, it was redissolved in tetrahydrofuran having the same mass as the coagulated product and coagulated again with a large amount of hexane. After this re-dissolution / coagulation operation was performed three times in total, the obtained coagulated product was vacuum-dried at 40 ° C. for 48 hours to obtain the intended component E-1.
The component composition of Component E-1 is shown in Table 2.

[Component (F)]
Methyl isobutyl ketone

[Preparation of coating composition for optical waveguide]
The above components (A) to (F) were uniformly mixed at the blending ratio shown in Table 3 to obtain an optical waveguide coating composition. In addition, the numerical value of Table 3 is an amount (unit: mass part) when the total amount of the component (A) to the component (F) is 100 parts by mass.

[2. Preparation of photocurable resin composition for optical waveguide body]
Opstar PJ3075 (manufactured by JSR) was prepared as a photocurable resin composition for forming the lower and upper clad layers. Opstar PJ3074 (manufactured by JSR) was prepared as a photocurable resin composition for forming a core.

[3. Formation of film-like optical waveguide]
[Example 1]
(1) Formation of first antistatic layer The optical waveguide coating composition was applied to the upper surface of a silicon substrate with a spin coater and prebaked at 100 ° C. for 10 minutes using a hot plate. Next, the coating film made of the coating composition J-1 for optical waveguides was irradiated with ultraviolet light having a wavelength of 365 nm and an illuminance of 10 mW / cm ² for 100 seconds to be photocured to obtain an antistatic layer having a thickness of 10 μm.
(2) Formation of lower clad layer A photocurable resin composition for forming a clad layer (OPSTAR PJ3075; manufactured by JSR) was applied to the upper surface of the antistatic layer with a spin coater, and was heated at 100 ° C. for 10 minutes using a hot plate. Pre-baked with conditions. Next, the coating film made of the photocurable resin composition for forming a clad layer was irradiated with ultraviolet rays having a wavelength of 365 nm and an illuminance of 10 mW / cm ² for 100 seconds to be photocured. The cured film was post-baked at 150 ° C. for 1 hour to form a lower cladding layer having a thickness of 10 μm.
(3) Formation of core portion A photocurable resin composition for core formation (OPSTAR PJ3074; manufactured by JSR) was applied onto the lower clad layer with a spin coater and prebaked at 100 ° C for 10 minutes. Next, an ultraviolet ray having a wavelength of 365 nm and an illuminance of 10 mW / cm ² is irradiated for 100 seconds to a 50 μm-thick coating film made of the core-forming photocurable resin composition through a photomask having a line pattern having a width of 50 μm. And photocured. And the board | substrate which has the hardened coating film was immersed in the developing solution which consists of acetone, and the unexposed part of the coating film was dissolved. Thereafter, post-baking was performed at 150 ° C. for 1 hour to form a core portion having a line pattern having a width of 50 μm.

(4) Formation of upper clad layer On the upper surface of the lower clad layer having a core portion, a photocurable resin composition for forming a clad layer (OPSTAR PJ3075; manufactured by JSR) was applied with a spin coater, and 100 ° C. using a hot plate. Pre-baking was performed for 10 minutes. Thereafter, the coating film made of the photocurable resin composition for forming the clad layer is photocured by irradiating with ultraviolet rays having a wavelength of 365 nm and an illuminance of 10 mW / cm ² for 100 seconds, and the thickness from the upper surface of the core portion is 10 μm A clad layer was formed.
(5) Formation of Second Antistatic Layer The optical waveguide coating composition was applied to the upper surface of the upper clad layer with a spin coater and prebaked at 100 ° C. for 10 minutes using a hot plate. Next, the coating film made of the photocurable resin composition was irradiated with ultraviolet rays having a wavelength of 365 nm and an illuminance of 10 mW / cm ² for 100 seconds to be photocured to obtain an antistatic layer having a thickness of 10 μm.
(6) Exfoliation of substrate The cured product formed in the steps (1) to (5) is exfoliated from the substrate, and the first antistatic layer, the lower cladding layer, the core portion, the upper cladding layer, and the second A film-like optical waveguide obtained by laminating antistatic layers in this order was obtained.

[Examples 2 to 4, Comparative Example 1]
A film-like optical waveguide was formed in the same manner as in Example 1 except that the component composition of the photocurable resin composition for forming the antistatic layer was changed as shown in Table 3.

[4. Evaluation of film-like optical waveguide]
Film-shaped optical waveguides (Examples 1 to 4, Comparative Example 1) were evaluated as follows.
[1. Antistatic property]
The measurement method defined in the column of resistivity of 5.13 of JISK6911 (1995 edition) under the environment of a temperature of 23 ° C. and a humidity of 50% on the surface on which the antistatic layer of the produced film-shaped optical waveguide is formed In accordance with the above, using a high resistance meter (Agilent Technology Co., Ltd. Agilent 4339B) and Resistivity Cell 16008B (Agilent Technology Co., Ltd.), surface resistivity (Ω / □) was measured.
“◯” when the surface resistivity of the film-shaped optical waveguide is 1 × 10 ¹² Ω / □ or less, “△” when 1 × 10 ¹² Ω / □ is exceeded and less than 1 × 10 ¹⁴ Ω / □, The case of 1 × 10 ¹⁴ Ω / □ or more was designated as “x”.
[2. Bending durability]
A bending test was performed on the produced film-shaped optical waveguide (width 1 cm, length 10 cm, thickness 90 μm) in an environment of a temperature of 23 ° C. and a humidity of 50%. The test conditions are a bending radius of 2 mm, a bending angle of ± 135 °, a bending speed of 100 times / minute, and a load of 100 g. The number of bendings was bent from the initial 0 degree position (the film-shaped optical waveguide was in a horizontal state) to a +135 degree position, and then bent again to a -135 degree position via the 0 degree position. Thereafter, the operation of returning to the 0 degree position is defined as one time. The number of times until the film-shaped optical waveguide breaks is measured, and “○” indicates that no breakage or crack occurs even if the number of bending exceeds 100,000, and breakage or crack occurs when the number of bending is less than 100,000. The case where it did was made "△".
The above results are shown in Table 3.

  From Table 3, it can be seen that the film-like optical waveguides of the present invention (Examples 1 to 4) are excellent in bending durability and antistatic properties. It can be seen that Comparative Example 1 in which the antistatic agent of component (D) is not blended is inferior in antistatic properties.

It is sectional drawing which shows typically an example of the film-form optical waveguide of this invention. It is a flowchart which shows an example of the manufacturing method of the film-form optical waveguide of this invention.

Explanation of symbols

2 Substrate 4 Thin film 6 Light 8 Antistatic layer 10 Lower clad layer 12 Thin film for core 14 Photomask 16 Light 18 Core portion 20 Upper clad layer 22 Antistatic layer 24 Film-like optical waveguide

Claims (4)

  A film-shaped optical waveguide having a lower cladding layer, a core portion, and an upper cladding layer, wherein the film-shaped optical waveguide has an antistatic layer on one or more surfaces of the lower cladding layer and the upper cladding layer Waveguide. The film-like optical waveguide according to claim 1, wherein the antistatic layer is obtained by curing a composition containing the following components (A) to (D).
(A) Urethane (meth) acrylate oligomer (B) Monomer having one or more (meth) acryloyl groups in the molecule (C) Photoradical polymerization initiator (D) Antistatic agent   The film form according to claim 1 or 2, wherein the (D) antistatic agent is at least one selected from the group consisting of a lithium-based antistatic agent, an ionic liquid antistatic agent, and a quaternary ammonium salt-based antistatic agent. Optical waveguide.   The film-like optical waveguide according to any one of claims 1 to 3, wherein the (A) urethane (meth) acrylate oligomer includes a reaction product of a polyol compound, a polyisocyanate compound, and a hydroxyl group-containing (meth) acrylate.

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