JPS62175703A - Organic siloxane optical waveguide and its production - Google Patents

Abstract

PURPOSE:To decrease the irradiation dose to cross-link all the liquid polymer in a supporting member made of a polymer which is long in the light transmission direction to a thoroughly crosslinked and cured body by providing the above-mentioned supporting member and an optical waveguide part consisting of an org. siloxane polymer to be filled into the space of said member. CONSTITUTION:The supporting member 11 made of the polymer which is long in the light transmission direction and has a closed space over the entire length and the transparent optical waveguide part 12 consisting of the org. siloxane polymer to be filled into the space thereof are provided. The optical waveguide part 12 is made of the transparent org. siloxane polymer and is suitable for light transmission. Crosslinking of the liquid polymer is not completely executed and therefore, the liquid or gel-like org. siloxane polymer is utilized as the optical waveguide part. The required radiation dose for irradiation is thereby made smaller than in the case of thoroughly crosslinking the entire part of the optical waveguide part. The cost of energy consumption is thus reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an optical waveguide having an optical waveguide made of an organic siloxane polymer and a method for manufacturing the same.

[Prior Art] An optical waveguide having an optical waveguide made of a liquid polymer and a support member made of a polymer is preferably used because of its excellent flexibility.

There are various types of such optical waveguides.
The figure shows an example of such a conventional optical waveguide.

FIG. 9 shows an optical waveguide in which an optical waveguide section 92 is formed by filling a polymer support member 91 with a liquid polymer and crosslinking the entire structure. In the drawings, the crosslinked and cured portions are indicated by diagonal lines, but all of the liquid polymer has been crosslinked and cured. In order to perform addition-type crosslinking or condensation-type crosslinking, methods such as addition of peroxide or chloroplatinic acid or heating are used.

However, both methods have drawbacks. Gas is generated when peroxide is added.

When chloroplatinic acid is added, absorption of light by the chloroplatinic acid occurs. When heating, the support member and the optical waveguide may separate from each other due to expansion and contraction of volume due to heating and cooling. As a result, optical transmission loss in the optical waveguide increases. Also,
A crosslinking method using radiation irradiation is used, but a large amount of radiation is required in order to completely cure the liquid polymer in the support member.

[Object of the Invention] An object of the present invention is to provide an optical waveguide that eliminates the above-mentioned drawbacks.

[Structure of the Invention] The gist of the present invention is as follows: (1) A polymeric support member that is long in the light transmission direction and has at least one closed space over its entire length; (2) An organic support member that fills the space in the polymer support member. at least one transparent optical waveguide consisting of a siloxane polymer; (3) optionally an intermediate layer between the support member and the optical waveguide; and (4) optionally within the optical waveguide and/or supporting The optical waveguide has a rod-like body and/or a tubular body existing in the part.

Other aspects of the invention include (1) a polymeric support member that is elongated in the direction of light transmission and that has at least one closed space over its entire length; (3) optionally an intermediate layer present between the support member and the optical waveguide; and (1) optionally within the optical waveguide and/or within the support member. A method for producing an optical waveguide having an optical waveguide having a rod-like body and/or a tubular body present in A light guide characterized in that, after filling at least one space of a buried and/or fixed polymer support member with a liquid organosiloxane polymer, the liquid organosiloxane polymer is at least partially crosslinked to form an optical waveguide. It has a method of manufacturing waves.

The polymer support member corresponds to a cladding in an optical fiber, and is made of a material having a smaller refractive index than the optical waveguide. Preferred materials include fluorine-containing polymers such as tetrafluoroethylene/hexafluoropropylene copolymers and polytetrafluoroethylene. Furthermore, polymers such as polychlorotrifluoroethylene, fluorine-containing polysiloxane, polyvinyl chloride, and polyethylene may be used, and dimethylsiloxane rubber having a relatively small refractive index may also be used. Rubber materials are preferred when flexibility is required.

When an intermediate layer is present, there is no restriction on the refractive index;
A polymer with excellent mechanical properties may be selected from all kinds of polymers, such as plastics and elastomers.

The shape of the polymer support member may be any shape such as a tube, a plate, or a tape. The shape of the support member for accommodating the optical waveguide is not limited to only a circle, but may be any other shape.

The optical waveguide is made of transparent organosiloxane polymer and is suitable for optical transmission. In the present invention, the liquid polymer is not completely crosslinked, and therefore a liquid or gel organic siloxane polymer is used as the optical waveguide. By doing so, the required irradiation radiation dose is smaller and the energy consumption cost is lower than when the entire liquid guide section is completely crosslinked. It is particularly preferable that the end portion of the optical waveguide portion is a crosslinked cured product, and the other portion is in a liquid or gel state. When the optical waveguide is liquid, the adhesion between the support member and the optical waveguide is good even when the optical waveguide is bent.

Moreover, when the optical waveguide is in gel form, liquid leakage from the optical waveguide does not occur. Any organic siloxane polymer may be used as the liquid polymer for forming the optical waveguide, but since a high refractive index can be obtained, dimethylsiloxane/diphenylsiloxane copolymer and dimethylnoroxane/methylphenylsiloxane copolymer are preferred. is preferred.

The optional intermediate layer is made of a material with a refractive index lower than that of the optical waveguide.

Examples of cases in which an intermediate layer is used include the following: When a polymer support member alone cannot sufficiently meet the requirements such as protection of the optical waveguide or mechanical strength; If it is not possible to obtain a support member with a refractive index smaller than that of the corrugated portion, or; Polymer support members are generally made by extrusion molding, but scratches on the inner surface of the polymer support member, surface roughness, etc. that occur during this process For example, when this adversely affects the transmission loss of light. Preferred materials for the intermediate layer include siloxane polymers, fluoronoxane polymers, fluorine-containing polymers, polyvinyl acetate, ethylene/vinyl acetate copolymers, polyvinyl acetals, and methyl cellulose. When using a material with poor flexibility such as plastic for the intermediate layer, it is difficult to satisfy the requirements for flexibility.
It is preferable to reduce the thickness of the intermediate layer.

The optional rod-shaped and/or tubular bodies are present inside the optical waveguide, inside the support element, or both. The rods and/or tubes are typically present over the entire length of the optical waveguide. However, it is not necessary that the rod-shaped body and/or the tubular body exist over the entire length of the optical waveguide; for example, the rod-shaped body and/or the tubular body are present in the central part in the longitudinal direction of the optical waveguide, and exit to the outside of the optical waveguide at the side surfaces of the ends of the optical waveguide. ing. Examples of rod-shaped bodies include image fibers, electric wires, and wires. An example of a tubular body is a pipe, and the space of the tubular body is used as a passage for fluid (such as liquid or gas) or as a hole for inserting an object. Rod-shaped bodies and tubular bodies are
In order to reduce absorption and scattering of light when it is inside the optical waveguide, it is preferable that the outside thereof be coated with a fluorine-containing polymer or the like.

To crosslink liquid organosiloxane polymers, radiation irradiation, crosslinking agents such as peroxides, crosslinking coagents such as platinum catalysts, or heating can be used.

Since impurities such as a crosslinking agent or a crosslinking aid cause absorption and scattering, a method using radiation irradiation is preferred. During radiation crosslinking, it is preferable to under-apply the radiation, that is, to reduce the irradiation dose and prevent gas generation. Radiation here refers to α rays, β rays, γ rays, X rays, and electron rays.

The present invention will be described below with reference to the accompanying drawings, but the invention is not limited to the embodiments shown in the drawings.

FIG. 1 is a cross-sectional view of an optical waveguide of the present invention having one optical waveguide. This optical waveguide is the simplest embodiment of the present invention and does not have an intermediate layer, rod-like bodies, or tubular bodies. The optical waveguide may be either liquid or gel. Polymer support member! The refractive index of 1 is smaller than the refractive index of the optical waveguide I2. Polymer support member 11
The optical waveguide section 12 is formed by filling the space with a liquid organic siloxane polymer and then irradiating at least a portion thereof with radiation. The degree of crosslinking of the organosiloxane can be controlled by the radiation dose, and the liquid organosiloxane polymer is not completely crosslinked and cured.

FIG. 2 is a longitudinal sectional view of the optical waveguide of the present invention, in which the degree of crosslinking at both ends of the optical waveguide is greater than the degree of crosslinking at the center.

By irradiating both ends of the liquid organic siloxane polymer filled in the supporting member 21 with a large amount of radiation, the degree of crosslinking of the optical waveguide section 22 is increased at both ends (shaded areas in the drawing). Both ends are completely crosslinked and cured. This prevents the liquid or gel organic siloxane polymer from leaking out of the optical waveguide.

Therefore, the ease of handling at the end of the optical waveguide is improved.

FIG. 3 is a cross-sectional view of an optical waveguide of the invention with an intermediate layer. The number of optical waveguides is one. An intermediate layer 33 is present between the polymeric support member 31 and the optical waveguide 32 .

The refractive index of the intermediate layer 33 is smaller than the refractive index of the optical waveguide section 32 . The refractive index of the polymer support member 31 is the same as that of the optical waveguide 32.
There is no need for the refractive index to be lower than that of , and there is a wide range of choices for polymeric support member materials. The intermediate layer 33 can be formed either simultaneously with the manufacture of the polymeric support member (e.g., by co-extrusion of the polymeric support member and the intermediate layer) or by coating the inner surface of the polymeric support member with the interlayer material after the polymeric support member has been manufactured. It can be manufactured by

Although an embodiment in which no intermediate layer is present will be described below, an intermediate layer may be present between the polymer support member and the optical waveguide.

4A and 4B are cross-sectional views of an optical waveguide of the present invention having a plurality of optical waveguide sections. The optical waveguide shown in FIG. 4A has two optical waveguide sections 42 inside a polymer support member 41.
The optical waveguide of FIG. 4B has a polymer support member 41.
' has three optical waveguide sections 42'. These optical waveguides are manufactured by filling all of a plurality of spaces of a polymer support member with a liquid organosiloxane polymer and crosslinking the liquid organosiloxane polymer. Although semicircular and circular optical waveguides are shown in the drawings, the cross-sectional shape of the optical waveguide may be any shape, for example, a polygon such as a triangle or a quadrangle. Furthermore, the cross-sectional shape of the optical waveguide is not limited to only circular or rectangular shapes, but may be any shape, and the optical waveguide may have a tape-like appearance. Further, the two optical waveguides do not need to be parallel, but may be spirally shaped.

5A-5D are cross-sectional views of optical waveguides of the present invention having at least one hole. Figures 5A and 5B
The illustrated optical waveguide has one optical waveguide section 52 or 52' and one cavity 53 or 53' inside the polymer support member 51 or 5. The optical waveguide of FIG. 5A and the fifth
The optical waveguide shown in Figure B differs in the shape of the holes. 5th C
The figure shows two optical waveguides 5 inside the polymer support member 5.
2'' and two holes 53''. These optical waveguides are formed by filling at least one space of a polymer support member having at least two spaces with a liquid organic loxane polymer and crosslinking the polymer to form an optical waveguide.
It is manufactured by leaving two spaces intact to form a void.

The number and shape of the optical waveguide and holes may be any and are not limited to the embodiments in the drawings. The holes can be used for various purposes, for example, as liquid or gas inlet holes, image fiber accommodation holes, and the optical waveguide of the present invention can be applied as a medical catheter. Further, depending on the purpose, electric wires, wires, etc. can be accommodated in the holes.

FIG. 5D is a cross-sectional view of the optical waveguide of the present invention used as a balloon-equipped vascular catheter.

This catheter is used for intravascular examinations.
An optical waveguide section inside the support part vr54 is used as a light guide 55 for sending illumination light, and is connected to a light source. 3
An image fiber 59 is inserted into the hole 56 of the two holes, and the other two holes 57 and 58 are used as a balloon inflation hole and a flash hole, respectively.

After inserting the tip of the catheter into a predetermined position within the blood vessel, liquid is injected into the balloon through the balloon inflation hole 57 to inflate the balloon and fix the catheter within the blood vessel. Blood in the blood vessel is removed by squirting a liquid (eg, physiological saline) from the flush hole 58. The inside of the blood vessel is illuminated by light sent through the illumination light guide 55. In this state, image fiber 5
9 to observe the inside of the blood vessel.

FIG. 6 is a cross-sectional view of the optical waveguide of the present invention in which a rod-like body and/or a tubular body are present within the optical waveguide. This optical waveguide has two tubular bodies and one rod-shaped body. This optical waveguide can also be used as a catheter, and has a support member 6I and an optical waveguide section 62 made of organic siloxane, and an image fiber 63 and two tubular bodies 64 and 64' are embedded inside the optical waveguide section 62. has been done. The tubular bodies 64 and 64' are used as conduits for injecting physiological saline to inflate the balloon within the blood vessel and for removing physiological saline or air from within the balloon, respectively.

This optical waveguide can be manufactured as follows: A tube 64, 64, and an image fiber 63 coated with polytetrafluoroethylene are inserted and positioned into the supporting member 61, which is the outermost shell. Positioning is done by attaching tubes 61, 64, 64' to positioning fittings (not shown).
This is done by fitting the image fibers 63 and applying a gentle tension to each of them and keeping them straight. next,
Two-component Noricon rubber (additive crosslinking type) is injected through a hole (not shown) provided at one end of the tube 61 to fill the inside of the tube 61 . After filling with silicone rubber, it is crosslinked and molded to form the catheter body. In addition to the catheter shown in FIG. 6, catheters simply used for endoscopy that do not have a tube 64.64° are also within the scope of the present invention, and the number of rod-shaped bodies and/or tubular bodies is not limited and may be any number. .

7A-70 are cross-sectional views of the optical waveguide of the present invention in which rod-shaped bodies and/or tubular bodies are present in the support member.

The optical waveguide shown in FIG. 7A has one optical waveguide section 72 and two rod-shaped bodies (for example, electric wires) 73 inside the support member 71, and the optical waveguide shown in FIG. The optical waveguide in FIG. 7C has two optical waveguides 72'' and two rods 73'' inside the support member 7bi, respectively.
and a tubular body 74". The rod and/or the tubular body is inside the support member and outside the optical waveguide. The optical waveguide is extruded together with the rod and/or the tubular body to form a space and a It can be manufactured by a method such as obtaining a polymer support member in which a tubular body and/or rod-like body is placed, then filling the space of the support member with a liquid polymer, and then curing the polymer support member.

Embodiments that combine FIGS. 6 and 7, ie, embodiments in which the rod-shaped body and/or the tubular body are present in the optical waveguide and in the support member, are also within the scope of the present invention.

Figures 8A and 8B are cross-sectional views of optical waveguides of the present invention in which liquid polymer and gel polymer are partially present (eg, over the entire length of the optical waveguide except at the distal end of the optical waveguide). In the drawings, portions that remain in liquid form are surrounded by dotted lines.

The optical waveguide 82 or 82° is the liquid portion 83 or 83
° and its outer gel-like part.

The liquid portion 83 in the embodiment shown in Fig. 8A and Fig. 8B.
The cross-sectional shape of the liquid portion 83° is different. The optical waveguide shown in FIG. 8A is constructed by irradiating an electron beam from all around the polymer support member 81 but not crosslinking the liquid siloxane polymer in the center, leaving a liquid portion 83 inside the optical waveguide 82. ing. Optical waveguide section 8 in FIG. 8B
2゛ is the polymer support +, tst' facing 2
It is formed by irradiating electron beams from two directions, and there is an elliptical liquid portion 83'. liquid part 8
The magnitudes of 3 and 83 degrees can be easily adjusted by adjusting the acceleration voltage of the electron beam. Alternatively, the positional relationship between the liquid portion and the gel portion may be reversed, and the gel portion may be present inside the liquid portion.

The optical waveguide body of the present invention can be used in catheters, light guides, illuminations, optical sensors, such as disconnection detection sensors for automobile lamps or object detection sensors, optical switches, counters, and the like.

[Example] Examples are shown below.

Example 1 A fluorinated ethylene/fluorinated propylene copolymer (FEP) tube with an inner diameter of 2 mm, an outer diameter of 3n++R and a length of 10 m was cleaned with a dust-free solvent and then washed with a weight average molecular fi1.
5xl O' of liquid polydimethylsiloxane was filtered through a 2 μm filter and filled into a tube. A 7 megarad electron beam is irradiated over a length of 20 cm at both ends of this tube to harden the liquid polydimethylsiloxane.
An optical waveguide was obtained.

The transmission loss is shown in Table 1.

Example 2 A tube obtained in the same manner as Example 1 was irradiated with an electron beam at 3Mra.
An optical waveguide was obtained by irradiating the tube with an electron beam of 4 Mrad over a length of 20 cm at both ends of the tube. The transmission loss is shown in Table 1.

Example 3 After cleaning a silicone rubber tube with an inner diameter of 4 mm, an outer diameter of 6 mm, and a length of 2 m with a dust-free solvent, it was washed with fluororubber Daiel G901 (n, = 1.36) manufactured by Daikin Industries, Ltd.
The weight percent methyl ketone solution was poured into a silicone rubber tube, and the solvent was thoroughly dried.

After performing this operation twice, liquid polydimethylsiloxane filtered through a 2 μm filter was filled into the tube.

An optical waveguide was obtained by irradiating an electron beam of 3 Mrad over the entire length of this tube, and then irradiating an electron beam of 4 Mrad over a length of 20 cm at both ends of the tube. The transmission loss is shown in Table 1.

Comparative Example 1 After washing a fluorinated ethylene/fluorinated propylene copolymer (FEP) tube with an inner diameter of 2 mm, an outer diameter of 3 mm, and a length of 10m with a dust-free solvent, a weight average molecular weight of 2xl was obtained.
CHa CH3 in liquid state at O' CH2=CH→5t-0→-S i CH= CHt
CHs CH3 and liquid HCH with a weight average molecular weight of 1.3xlO'.

A mixture with a weight ratio of 4:1 was filtered through a 2 μm filter and filled into a tube. Put this in the furnace for 200
The polymer mixture was cured by heat treatment at .degree. C. for 12 hours. After cooling to room temperature, the tube was removed from the furnace.
Peeling occurred throughout the tube. Table 1 shows the transmission loss of this optical waveguide.

Comparative Example 2 KEI06 manufactured by Shin-Etsu Chemical Co., Ltd. (polydimethylsiloxane with vinyl groups at both ends, viscosity 40 voids, pale yellow transparent liquid)
and CAT-RG (dimethylsiloxane/methylhydrogensiloxane copolymer, colorless transparent liquid) manufactured by the same company were each filtered and mixed at a weight ratio of 1 ol. This mixture was filled into a PEP tube with an inner diameter of 2 mm, an outer diameter of 3 mm, and a length of 5 m that had been cleaned with a dust-free solvent and cured at room temperature. Table 1 shows the transmission loss of the obtained optical waveguide.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of an optical waveguide of the present invention in which one leading liquid section is suspended. FIG. 2 is a cross-sectional view of an optical waveguide according to the present invention in which the degree of crosslinking at both ends of the leading liquid section is greater than that at the center. FIG. 3 is a cross-sectional view of an optical waveguide of the present invention having an intermediate layer; FIGS. 4A and 4B are cross-sectional views of an optical waveguide of the present invention having a plurality of guide liquid parts. 5A to 5D are cross-sectional views of an optical waveguide of the invention having at least one hole; FIG. 7A to 70 are cross-sectional views of the optical waveguide of the present invention in which rod-like bodies and/or tubular bodies are present in the support member; FIGS. 8A and 8B are cross-sectional views of liquid polymer and gel FIG. 9 is a cross-sectional view of an optical waveguide of the present invention in which a shaped polymer is present over the entire length. FIG. 9 is a longitudinal cross-sectional view of a conventional optical waveguide. f 1, 21, 31.41.41', 51, 51°, 5
1". 54.61, 71.71', 7bi, 81, 83°, 91
... Polymer support member, 12.22.32, 42.42°, 52, 52°, 52
°. 55.62, 72, 72°, 72", 82.82', 9
2-... Leading liquid part, 33... Intermediate layer, 53.53°, 53°, 56, 57.58... Holes,
59.63, 73, 73°, 73"...rod-shaped body, 64.
64', 74°, 74"...Tubular body, 83°83'.
...Liquid part. Patent Applicant Sumitomo Electric Industries Co., Ltd. Representative Patent Attorney 2 people Figure 1 Figure 2 Figure 3 Figure 4A Figure 48 Figure 5A Figure 58 Figure 6 Figure 70

Claims (1)

[Claims] 1. (1) A polymer support member that is elongated in the light transmission direction and has at least one closed space over its entire length; (2) An organic siloxane polymer that fills the space in the polymer support member. at least one optical waveguide that is transparent; (3) an intermediate layer optionally present between the support member and the optical waveguide; and (4) optionally present within the optical waveguide and/or within the support member. An optical waveguide having a rod-shaped body and/or a tubular body. 2. The optical waveguide according to claim 1, wherein the optical waveguide portion is a cross-linked cured product or a gel-like material. 3. The optical waveguide according to claim 1, wherein the optical waveguide portions have partially different degrees of crosslinking. 4. The optical waveguide according to claim 3, wherein the end portion of the optical waveguide portion is a crosslinked cured product, and the other portion is in a liquid or gel state. 5. The optical waveguide according to any one of claims 1 to 4, having at least two independent optical waveguide sections. 6. Claim 1 having at least one hole
The optical waveguide according to any one of items 1 to 5. 7. The optical waveguide according to any one of claims 1 to 6, wherein the polymer support member has a smaller refractive index than the optical waveguide. 8. The optical waveguide according to any one of claims 1 to 7, wherein the refractive index of the intermediate layer is smaller than the refractive index of the optical waveguide. 9. (1) a polymer support member elongated in the direction of light transmission having at least one closed space along its entire length; (2) at least one transparent light guide made of an organosiloxane polymer filling the space in the polymer support member; (3) an intermediate layer that is optionally present between the support member and the optical waveguide; and (4) a rod and/or that is optionally present within the optical waveguide and/or within the support member. A method for manufacturing an optical waveguide with an optical waveguide having a tubular body, optionally with an intermediate layer on its inner surface, with the tubular body and/or the rod optionally embedded and/or fixed in position with a polymer. A method for manufacturing an optical waveguide, comprising filling at least one space of a support member made of liquid with a liquid organic siloxane polymer, and then at least partially crosslinking the liquid organic siloxane polymer to form an optical waveguide. 10. The method for producing an optical waveguide according to claim 9, wherein the liquid organic siloxane polymer is made into a crosslinked cured product or a gel. 11. The manufacturing method according to claim 9, wherein the degree of crosslinking of the liquid organosiloxane polymer is partially changed. 12. The manufacturing method according to claim 11, wherein the degree of crosslinking of the liquid organosiloxane polymer is increased at the end of the optical waveguide. 13. The polymer support member before forming the optical waveguide has at least two spaces, and at least one space is filled with a liquid organosiloxane polymer, according to any one of claims 9 to 12. Manufacturing method. 14. The manufacturing method according to any one of claims 9 to 13, wherein the polymer support member has a smaller refractive index than the optical waveguide. 15. The manufacturing method according to any one of claims 9 to 14, wherein the refractive index of the intermediate layer is smaller than the refractive index of the optical waveguide. 16.Claim No. 9 in which crosslinking is performed by radiation irradiation
The manufacturing method according to any one of items 1 to 15.