JP2014087541A - Transparent structure and endoscope made using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent structure having excellent visibility and an endoscope made using the same.SOLUTION: A transparent structure is made by disposing a body fluid component adhesion preventing layer having hydrophobic fine particles on at least part of a surface of a transparent base material, and the transparent structure is used as an endoscope lens cover.

Description

  The present invention relates to a transparent structure and an endoscope using the same. In particular, the present invention relates to a transparent structure excellent in visibility and an endoscope using the same.

  Currently, endoscopes are used to observe and diagnose various internal parts of the human body, including the digestive system such as the esophagus, stomach, intestines, ears, nose, throat, lungs, urethra, bladder, kidneys and uterus. ing. When a lesion is found by observation / diagnosis, it is possible to remove the lesion or collect cells on the spot using a treatment tool installed at the tip of the endoscope. became. These procedures are minimally invasive procedures that do not involve surgery. In addition, in recent years, endoscopic surgery is performed by surgical treatment with surgical instruments and electric scalpels while making small holes in the abdomen and chest and observing the body cavity with an endoscope such as a laparoscope Has been done. Unlike conventional surgical operations, this technique is used very frequently at the point that the burden on the patient's body can be greatly reduced and the QOL (Quality Of Life) of the patient can be greatly improved.

  In general, an endoscope observes and treats the inside of a body cavity through an objective lens provided at a distal end portion, but mucus or tissue in the body adheres to the objective lens, and visibility decreases, Treatment may not be successful. For this reason, a lens cleaning nozzle is arranged toward the objective lens, and a cleaning liquid, air, or the like is sprayed from the nozzle to clean the lens surface, thereby securing a field of view (for example, Patent Document 1). .

JP-A-2-129613

  However, even with such a lens cleaning nozzle, it is difficult to clean the lens completely. In addition, the cleaning liquid may adhere to the lens surface and conversely reduce visibility. In addition, due to the necessity of such a lens cleaning nozzle, it is difficult to reduce the diameter of the endoscope, and when inserting the endoscope through the patient's living body lumen, the endoscope reduces the living body lumen. The pressure is on and the patient is painful.

  Therefore, the present invention has been made in view of the above circumstances, and an object thereof is to provide a transparent structure excellent in visibility and an endoscope using the same.

  Another object of the present invention is to provide an endoscope that does not require a lens cleaning nozzle.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problem can be solved by arranging hydrophobic fine particles on at least a part of the surface of the transparent substrate. Completed the invention.

  That is, the above object can be achieved by a transparent structure in which a body fluid component adhesion preventing layer having hydrophobic fine particles is disposed on at least a part of the surface of a transparent substrate.

  According to the transparent structure of the present invention, it is possible to effectively suppress and prevent body fluids such as mucus and blood from adhering to the surface. For this reason, when the transparent structure of the present invention is used as an endoscope lens cover, the adhesion of body fluid components (mucus, blood, etc.) derived from a living body can be effectively suppressed / prevented even without a cleaning operation, thereby providing good visibility. It can be secured.

FIG. 1 is an enlarged cross-sectional view of a transparent structure according to a preferred embodiment of the present invention. FIG. 2 is an enlarged cross-sectional view of a transparent structure according to a preferred embodiment of the present invention. 3A is an SEM photograph of the surface of the body fluid component adhesion preventing layer of the transparent structure (1) of Example 1, and FIG. 3B is a laser of the surface of the body fluid component adhesion preventing layer of the transparent structure (1) of Example 1. It is a three-dimensional observation image by a microscope. FIG. 4 is a photograph of the transparent structure (1) of Example 1 before and after evaluation of blood contamination prevention ability. 5A is an SEM photograph of the surface of the body fluid component adhesion preventing layer of the transparent structure (2) of Example 2, and FIG. 5B is a laser of the surface of the body fluid component adhesion preventing layer of the transparent structure (2) of Example 2. It is a three-dimensional observation image by a microscope. FIG. 6 is a photograph of the transparent structure (2) of Example 2 before and after evaluation of the ability to prevent blood contamination. 7A is an SEM photograph of the surface of the body fluid component adhesion preventing layer of the transparent structure (3) of Example 3, and FIG. 7B is a laser of the surface of the body fluid component adhesion preventing layer of the transparent structure (3) of Example 3. It is a three-dimensional observation image by a microscope. FIG. 8 is a photograph of the transparent structure (3) of Example 3 before and after evaluation of blood contamination prevention ability. 9A is an SEM photograph of the surface of the body fluid component adhesion preventing layer of the transparent structure (4) of Example 4, and FIG. 9B is a laser of the surface of the body fluid component adhesion preventing layer of the transparent structure (4) of Example 4. It is a three-dimensional observation image by a microscope. FIG. 10 is a photograph of the transparent structure (4) of Example 4 before and after evaluation of the ability to prevent blood contamination. 11A is a SEM photograph of the surface of the body fluid component adhesion preventing layer of the transparent structure (5) of Example 5, and FIG. 11B is a laser of the surface of the body fluid component adhesion preventing layer of the transparent structure (5) of Example 5. It is a three-dimensional observation image by a microscope. FIG. 12 is a photograph of the transparent structure (5) of Example 5 before and after evaluation of the ability to prevent blood contamination. FIG. 13 is a graph showing the frequency variation in the albumin aqueous solution of the QCM electrode on which the transparent structure (6) of Example 6 and the transparent base material on which the body fluid adhesion preventing layer is not formed are arranged. FIG. 14 is a cross-sectional view schematically showing the configuration of a transparent structure according to a preferred embodiment of the present invention. FIG. 15 is an enlarged cross-sectional view showing an outline of the configuration of the distal end portion of the endoscope according to a preferred aspect of the present invention. FIG. 16 is a schematic diagram of the durability evaluation test apparatus (friction measuring machine) used in Example 7. FIG. 17 is a graph showing the results of durability evaluation in Example 7.

  The present invention relates to a transparent structure in which a body fluid component adhesion preventing layer having hydrophobic fine particles is disposed on at least a part of the surface of a transparent substrate. Conventionally, when observing a living body lumen or body cavity using an endoscope, a body fluid component (mucus, blood, etc.) or a cleaning liquid derived from a living body adheres to the lens surface even while the lens surface is being cleaned. And visibility may fall. In this case, it is necessary to take the endoscope out of the body and clean the surface, but this is not preferable because it increases the burden on the patient. In contrast, when the hydrophobic fine particles are arranged on the surface of the transparent substrate as in the present invention, the adhesion of body fluid components (mucus, blood, etc.) derived from living bodies to the lens surface is suppressed even without washing. In other words, good visibility during the operation can be ensured without performing the cleaning operation. Here, the mechanism of exerting the body fluid component adhesion preventing ability due to the arrangement of the hydrophobic fine particles is unknown, but is assumed as follows. Note that the present invention is not limited to the following estimation. That is, the surface of the transparent substrate on which the hydrophobic fine particles are arranged has a fine concavo-convex structure with high roughness (many concavoconvexities). Here, even if the fine concavo-convex structure is in contact with the liquid, air exists in the concave portion, so there is an interface with air between the adjacent convex portions, and the substrate surface-liquid surface is apparently in contact with a wide area. In addition, point contact is made by the presence of a large number of voids through which the liquid level cannot enter (the actual contact area with the droplet is small). And since the amount of increase in the actual free surface energy is small compared to the amount of increase in the surface area of water for water to adsorb on the surface, the body fluid components (mucus, blood, etc.) are more likely to spread on the surface with high roughness. Maintains the shape of the droplet and exhibits hydrophobicity by surface tension. Such a relationship is the contact of water with an inhomogeneous surface in which two different surfaces, an interface with air and another surface, coexist with the Wenzel equation indicating the relationship between the surface roughness and the contact angle of water. This can be explained by Cassie's equation for explaining the corners. Therefore, a surface with high roughness (fine concavo-convex structure) formed by hydrophobic fine particles can exhibit super water repellency with a contact angle of 150 ° C. or more. For this reason, when the transparent structure of the present invention is used as a lens cover for an endoscope or the like, it effectively suppresses / prevents the attachment of body fluid components (mucus, blood, etc.) derived from a living body even without a cleaning operation, and provides good visual recognition. The endoscope can be smoothly introduced to a predetermined site.

  Therefore, by installing the transparent structure of the present invention as a lens cover on the surface of the endoscope lens, it is possible to maintain a good visual field, reduce the stress on the operator, and shorten the procedure time. Can also reduce the burden.

  Embodiments of the present invention will be described below. In addition, this invention is not limited only to the following embodiment. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.

  In the present specification, “X to Y” indicating a range means “X or more and Y or less”, and “weight” and “mass”, “wt%” and “mass%”, “part by weight” and “ “Part by mass” is treated as a synonym. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

[Transparent substrate]
The transparent substrate that can be used in the present invention is not particularly limited as long as it is transparent, and transparent substrates generally used in the medical field can be used in the same manner. In the present specification, “transparent” means transparency to the extent that sufficient visibility can be achieved. Specifically, the “transparency” means a material that exhibits a visible light transmittance of preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more. . Considering that the body fluid component adhesion preventing layer is formed, the transparent substrate is a group having a visible light transmittance of 65% or more, more preferably 75% or more, and particularly preferably 85% or more (upper limit: 100%). Means wood. In the present specification, “visible light transmittance” is a value measured by the method described in the following examples.

  Specifically, methacrylic resin such as polymethyl methacrylate (PMMA) and methyl methacrylate-styrene copolymer, styrene resin such as polystyrene and styrene-acrylonitrile copolymer, epoxy resin, polycarbonate resin, polyester resin, high density polyethylene , Polysulfone, polyethersulfone, polyetherimide resin, acrylic resin, polymethylpentene, polyvinyl chloride resin, polycyclohexadiene, polyester, 1,3-cyclohexadiene homopolymer, 1,3-cyclohexadiene, 1,3 -Chain conjugated diene monomers such as butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, styrene, α-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene , Vinyl aromatic monomers such as vinyl styrene, polar vinyl monomers such as methyl methacrylate, methyl acrylate, acrylonitrile, methyl vinyl ketone, methyl α-cyanoacrylate, ethylene oxide, propylene oxide, cyclic lactone, cyclic lactam, cyclic siloxane Polymer materials such as polar monomers such as ethylene, and copolymers with ethylene and α-olefin monomers (copolymers described in JP-A-9-277045); glass and the like. In the present invention, the transparent substrate may be used as it is, but it is preferable to remove oils and dirt adhered to the surface of the transparent substrate before disposing the body fluid component adhesion preventing layer.

  Although it will not restrict | limit especially if the thickness of a transparent base material is a grade which can ensure transparency, It is preferable that it is 0.01-10 mm, and it is more preferable that it is 0.1-2 mm. With such a thickness, sufficient transparency is exhibited, and the lens surface can be well protected even if it is installed as a lens cover on the endoscope lens surface.

[Body fluid component adhesion prevention layer]
In the present invention, the body fluid component adhesion preventing layer is formed by arranging hydrophobic fine particles on at least a part of the surface of the transparent substrate. Here, the body fluid component adhesion preventing layer may be disposed on at least a part of the surface of the transparent substrate as long as the desired body fluid component adhesion preventing effect can be achieved. The ratio of the adhesion prevention layer formation area is preferably 50% or more, more preferably 80% or more (upper limit: 100%).

  The material of the hydrophobic fine particles is not particularly limited, but a substance having a small surface free energy is preferably used. Inorganic hydrophobic fine particles, organic hydrophobic fine particles and the like in which the surface of the inorganic oxide fine particles is modified with a hydrophobic functional group are hydrophobic fine particles. Can be used as

Among these, inorganic oxide fine particles are not particularly limited, but inorganic such as zinc oxide, titanium oxide (titania), silicon oxide (silica), zirconium oxide (zirconia), aluminum oxide (alumina), cerium oxide (ceria), etc. Examples thereof include fine particles of oxide. Commercially available products may be used as the inorganic oxide fine particles. Commercially available products include AEROSIL (registered trademark) 50, 90, 90G, 130, 200, 200V, 200CF, 200FAD, 255, 300, 300CF, 380, OX50, TT600, 200SP, 300SP, 300/30, MOX80, MOX170, Silica fine particles such as COK84 (all manufactured by Nippon Aerosil Co., Ltd.); Alumina fine particles such as aluminum oxide C, AEROXIDE (registered trademark) AluC, Alu65, Alu130 (all manufactured by Nippon Aerosil Co., Ltd.); Titanium dioxide T805, dioxide dioxide titanium P25, AEROXIDE _{(TM) TiO 2 P25, TiO 2 PF2} ( both produced by Nippon Aerosil Co., Ltd.) titania fine particles such as; FINEX-30, 50 (manufactured by Sakai Chemical Industry Co., Ltd.) zinc oxide fine such ; SZR (manufactured by Sakai Chemical Industry Co., Ltd.) such as zirconium oxide fine particles. The inorganic oxide fine particles may be used alone or in the form of a mixture of two or more. Further, the hydrophobic functional group is not particularly limited, but is a perfluoroalkyl group having 1 to 12 carbon atoms such as a trifluoromethyl group (—CF ₃ ); a methyl group, an ethyl group, an n-propyl group, an isopropyl group. , N-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, cyclohexyl, 1,3- Dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropyl group, 1- A linear, branched or cyclic alkyl group having 1 to 30 carbon atoms such as ert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, etc., preferably 1 carbon atom -18 linear or branched alkyl group; trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, dimethylisopropylsilyl group, diethylisopropylsilyl group, dimethylbutylsilyl group, t-butyldimethyl group A trialkylsilyl group (—Si (R) ₃ : R, such as a silyl group, a di-t-butylmethylsilyl group, or a tricyclohexylsilyl group, is independently a linear or branched chain having 1 to 30 carbon atoms. A chain or cyclic alkyl group, preferably a linear or branched alkyl group having 1 to 12 carbon atoms); Dialkylsilyl groups (such as rusilyl group, diethylsilyl group, di-n-propylsilyl group, diisopropylsilyl group, di-n-butylsilyl group, di-t-butylsilyl group, diisobutylsilyl group, methylethylsilyl group, methylisopropylsilyl group) —Si (R ′) ₂ H: R ′ each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms, preferably a linear or branched chain having 1 to 8 carbon atoms. Methylsilyl group, ethylsilyl group, n-propylsilyl group, isopropylsilyl group, n-butylsilyl group, t-butylsilyl group, isobutylsilyl group, pentylsilyl group, hexylsilyl group, 2-ethylhexylsilyl group , octylsilyl group, a dodecyl silyl group, an alkylsilyl group _{(-Si (R ') H 2} : R' Each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms, preferably a linear or branched alkyl group having 1 to 8 carbon atoms); a fluorosilyl group (- Si (R ″) _n (F) _3-n : R ″ each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms, preferably a straight chain having 1 to 8 carbon atoms. A chain or branched chain alkyl group, and n is an integer of 0 to 2); and a fluorine atom. One of the hydrophobic functional groups may be used for modification, or two or more may be used for modification. The ratio of substitution of the functional groups on the surface of the inorganic oxide fine particles (for example, silanol groups in the case of silica fine particles) with the hydrophobic functional groups is not particularly limited as long as the hydrophobicity can be imparted to the inorganic oxide fine particles. Preferably, 5 mol% or more, more preferably 10 mol% or more, more preferably 20 mol% or more (upper limit: 100 mol%) of the functional group on the surface of the inorganic oxide fine particle is modified with the hydrophobic functional group. In addition, the modification method (introduction method) of the inorganic oxide fine particles with the hydrophobic functional group is not particularly limited, and a known method such as silylation treatment can be applied in the same manner or appropriately modified.

Commercially available products may be used as the inorganic oxide fine particles (inorganic hydrophobic fine particles) surface-modified with the hydrophobic functional group. As commercially available products, AEROSIL (registered trademark) R972, R974, R972V, R972CF, R974, R805, R812, R812S, R504, RX50, NAX50, RX200, RX300, RY50, NY50, RY200, RY200S, R104, R106, R202, Hydrophobic silica fine particles such as R816, R7200, R8200, R9200, R711 (all manufactured by Nippon Aerosil Co., Ltd.); AEROXIDE (registered trademark) TiO ₂ T805, TiO ₂ NKT90 (all manufactured by Nippon Aerosil Co., Ltd.), etc. Hydrophobic titania fine particles; hydrophobic alumina fine particles such as AEROXIDE (registered trademark) AluC 805 (manufactured by Nippon Aerosil Co., Ltd.); FINEX-30S-LP2, 30W-LP2, 50S-LP2, 0 W-LP2 such hydrophobic zinc oxide fine particles (manufactured by Sakai Chemical Industry Co., Ltd.) and the like. Of these, AEROSIL (registered trademark) R972, RX200, and RX300 are preferable.

  Organic hydrophobic fine particles include polytetrafluoroethylene (PTFE), polystyrene (PS), polymethyl methacrylate (PMMA), polyethylene (PE), polypropylene (PP), polycarbonate (PC), polyethylene terephthalate (PET). , Organic fine particles such as polyimide (PI), vinyl chloride (PVC), and cellulose. As the organic hydrophobic fine particles, commercially available products may be used. The organic hydrophobic fine particles may be used alone or in the form of a mixture of two or more.

  The inorganic oxide fine particles (inorganic hydrophobic fine particles) and organic hydrophobic fine particles whose surface has been modified with the hydrophobic functional group described above, particularly when used in vivo, have halogen atoms, particularly fluorine atoms, in consideration of safety. It is preferably not included.

  The size of the hydrophobic fine particles is not particularly limited as long as the transparent base material can exhibit a body fluid component adhesion preventing ability. Specifically, the average particle size of the hydrophobic fine particles (average particle size (diameter) of primary particles) is preferably in the range of 5 to 300 nm, and more preferably in the range of 10 to 100 nm. Hydrophobic fine particles of such a size can impart a sufficiently high surface roughness (fine concavo-convex structure) to the transparent structure, so that the transparent structure is composed of biological fluid components (mucus, blood, etc.) Adhesion can be effectively suppressed / prevented. Moreover, if the hydrophobic fine particles have the above-described size, sufficient transparency can be ensured as a whole even when a plurality of fine particles are deposited, so that good visibility can be achieved. In the present specification, “particle diameter” means the maximum distance among any two points on the particle outline. “Average particle size of hydrophobic fine particles (average particle size (diameter) of primary particles)” is a statistically sufficient number of samples (for example, several hundred to several thousand samples) using a scanning electron microscope (SEM). And an average value of particle diameters obtained using an observation means such as a transmission electron microscope (TEM).

  Moreover, the arrangement | positioning form of hydrophobic fine particles on the transparent base material surface will not be restrict | limited especially if a transparent base material can exhibit a bodily fluid component adhesion preventing ability. Specifically, a mode in which the hydrophobic fine particles 3 are arranged in layers on the transparent substrate 2 to form the body fluid component adhesion preventing layer 5 (FIG. 1A); the hydrophobic fine particles 3 are in and on the transparent substrate 2 Form in which layered body fluid component adhesion preventing layer 5 is formed (FIG. 1B); body fluid component adhesion preventing layer 5 in which hydrophobic fine particles 3 are disposed in intermediate layer 4 formed on transparent substrate 2 Form (FIG. 1C): Form in which hydrophobic fine particles 3 are arranged on the entire surface of transparent base material 2 having groove 6 to form body fluid component adhesion preventing layer 5 (FIG. 1D); Transparent base material having groove 6 The intermediate layer 4 is formed over the entire surface, and the hydrophobic fine particles 3 are arranged on the entire intermediate layer 4 to form the body fluid component adhesion preventing layer 5 (FIG. 1E); the hydrophobic fine particles 3 have a groove 6 and are transparent Preferentially placed in the groove (recess) 6 of the substrate 2 to prevent body fluid component adhesion 5 (FIG. 2F); the intermediate layer 4 is formed over the entire surface of the transparent substrate 2 having the groove 6, and the hydrophobic fine particles 3 are selectively disposed in the groove (recess) 6 of the transparent substrate 2. Form for forming body fluid component adhesion preventing layer 5 (FIG. 2G); intermediate layer 4 having groove 6 is formed on transparent substrate 2, and hydrophobic fine particles 3 are arranged in groove (recess) 6 and intermediate layer 4 as a whole. Then, the form for forming the body fluid component adhesion preventing layer 5 (FIG. 2H); and the intermediate layer 4 having the groove 6 are formed on the transparent substrate 2, and the groove (recess) 6 and the intermediate layer 4 of the intermediate layer 4 are formed. Examples include a mode in which the hydrophobic fine particles 3 are selectively arranged to form the body fluid component adhesion preventing layer 5 (FIG. 2I). When the transparent structure has an intermediate layer, at least a part of the hydrophobic fine particles is exposed on the surface of the intermediate layer as shown in FIGS. 1C and 1E so that a fine uneven structure can be obtained. Preferably it is. Moreover, in FIG. 2G, the intermediate layer 4 does not need to completely cover the groove 6, and for example, the intermediate layer 4 may cover a part of the groove 6 as shown in FIG. 2J. A similar configuration applies to FIG. 1E. Further, in FIG. 2H, the hydrophobic fine particles 3 do not need to be disposed even in the intermediate layer 4, and may be selectively disposed on the surface of the intermediate layer 4 as shown in FIG. 2K, for example. A similar configuration applies to FIG. 2I.

  In the present specification, the portion where the hydrophobic fine particles are arranged is the “body fluid component adhesion preventing layer”. Therefore, as shown in FIG. 1C and the like, when the intermediate layer 4 is provided on the transparent substrate 2, the intermediate layer 4 including the hydrophobic fine particles 3 is also a body fluid component adhesion preventing layer 5.

  Among the above forms, a form (for example, FIGS. 1D to 2J) in which the transparent structure has a groove (concave portion) is preferable. That is, the transparent base material or body fluid component adhesion preventing layer preferably has a groove. Thus, by having a groove part, the hydrophobic fine particle which exists in a groove part fully exhibits the bodily fluid component adhesion prevention effect and a water-repellent effect. Even when the surface of the transparent structure is in contact with a living tissue (for example, the inner wall of a lumen), the hydrophobic fine particles are present in the groove (recessed portion) and are hardly detached. For this reason, since the hydrophobic fine particles present in the groove portion exhibit the ability to prevent body fluid component adhesion, the transparent structure of the present invention can exhibit the body fluid component adhesion preventing effect over a long period of time and is excellent in durability. Here, the arrangement form of the groove portions (the size and spacing of the groove portions) is not particularly limited as long as the above effect can be achieved, and can be appropriately selected depending on the size of the hydrophobic fine particles. For example, the arrangement state of the groove is not particularly limited, and various arrangement states such as a square lattice, a staggered lattice, and a hexagonal lattice can be employed. Further, the width of the groove (“D” in FIG. 1D) is preferably in the range of 0.1 to 200 μm, and more preferably in the range of 5 to 100 μm. In addition, the depth of the groove (“H” in FIG. 1D) is preferably in the range of 0.1 to 50 μm, and more preferably in the range of 1 to 25 μm. Furthermore, the interval between the groove portions (“R” in FIG. 1D) is preferably in the range of 0.1 to 600 μm, and more preferably in the range of 10 to 500 μm. Among these requirements, the width, depth, and interval of the groove are important from the viewpoints of body fluid component adhesion preventing effect, water repellency, and durability. That is, it is preferable that a transparent base material or a bodily fluid component adhesion prevention layer has a groove part with a space | interval of 0.1-600 micrometers, a width of 0.1-200 micrometers, and a depth of 0.1-50 micrometers on the surface. In addition, the space | interval of a groove part shows the distance between the edge parts of two adjacent convex parts, as shown by "R" of FIG. 1D. Thus, by arranging the hydrophobic fine particles in the groove portions of a specific size at specific intervals, a sufficient amount of hydrophobic fine particles are present in the groove portions. For this reason, the hydrophobic fine particles present in the grooves sufficiently exhibit the body fluid component adhesion preventing effect and the water repellent effect. Even when the surface of the transparent structure is in contact with a living tissue (for example, the inner wall of a lumen), the hydrophobic fine particles are present in the groove (recessed portion) and are hardly detached. For this reason, the transparent structure of the present invention can exhibit a body fluid component adhesion preventing effect over a long period of time, and can improve durability.

  Or the form (for example, FIG. 1C, FIG. 1E, FIG. 2G-FIG. 2K) by which an intermediate | middle layer is formed on a transparent base material among the said forms is also preferable. By arranging the hydrophobic fine particles in and on the intermediate layer in this way, even if the surface of the transparent structure comes into contact with the living tissue (for example, the inner wall of the lumen), the hydrophobic fine particles are at least partially embedded in the intermediate layer. Therefore, the hydrophobic fine particles are hardly peeled off even by friction. Therefore, the transparent structure having such a configuration can exhibit a body fluid component adhesion preventing effect over a long period of time and can improve durability. In addition, one of the major problems in the practical application of super-water-repellent surfaces has been the weakness of the structure. By arranging hydrophobic fine particles in the intermediate layer in this way, The strength can also be improved.

  Here, when the intermediate layer, particularly the intermediate layer contains hydrophobic fine particles, the thickness of the body fluid component adhesion preventing layer is not particularly limited, but the film strength, the retention of hydrophobic particles, the body fluid component adhesion preventing effect, In consideration of aqueousness, durability, etc., it is preferably 0.01 to 100 μm, more preferably 0.05 to 50 μm. Further, as shown in FIGS. 1A and 1B, the thickness of the body fluid component adhesion preventing layer is not particularly limited when only the hydrophobic fine particles are disposed on the transparent substrate to form the body fluid component adhesion preventing layer. In consideration of retention of hydrophobic fine particles, body fluid component adhesion preventing effect, water repellency, durability and the like, it is preferably 0.01 to 20 μm, more preferably 0.05 to 10 μm.

  In addition, when the intermediate layer, particularly when the intermediate layer contains hydrophobic fine particles, the body fluid component adhesion preventing layer can improve the retention of hydrophobic fine particles, adhesion to a transparent substrate, body fluid component adhesion prevention, durability, etc. In view of the above, it is preferable to include a binder resin. The binder resin is not particularly limited, and binder resins generally used in the medical field can be used. Specifically, acrylic resin such as alkyd resin, poly (meth) acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate, butyl poly (meth) acrylate, amino resin, polyurethane resin, Epoxy resin, silicone resin, fluororesin, acrylic silicone resin, unsaturated polyester resin, UV curable resin, phenol resin, vinyl chloride resin, styrene-acrylic resin, acrylonitrile-acrylic resin, vinyl acetate resin, vinyl acetate-acrylic resin, acetic acid Examples thereof include vinyl-vinyl chloride resin. In the intermediate layer (body fluid component adhesion preventing layer) containing these binder resins, hydrophobic fine particles can be better retained (embedded) (binder resin and hydrophobic fine particles can be well adhered), and body fluid components The adhesion preventing effect, water repellency, durability and the like can be further improved. In addition, when a hydrophobic binder resin is used, the intermediate layer (the body fluid component adhesion preventing layer if it contains hydrophobic fine particles) itself also exhibits higher water repellency, thus improving the body fluid component adhesion preventing effect and water repellency. it can. Moreover, since the said binder resin exhibits high transparency when it is set as a film | membrane, it is preferable also from a viewpoint of visibility. That is, the body fluid component adhesion preventing layer particularly preferably contains a binder resin.

  Here, the binder resin preferably has a contact angle of 45 degrees or more with the water of the binder resin in consideration of the body fluid component adhesion preventing effect, water repellency, durability, and the like. More preferably, the contact angle of the binder resin is 60 to 130 degrees. Here, the contact angle of the binder resin is measured using a general contact angle meter on the surface on which the binder resin is formed with a film having a thickness of 5 to 20 μm by dip coating, spin casting, spraying, or the like. Is the value to be Note that the contact angle of the binder resin does not change depending on the film thickness. Therefore, the film thickness can be appropriately selected depending on the binder resin used. More specifically, the contact angle is defined as the angle at which the droplet contacts the solid when the droplet is placed on the solid plate, and the curved surface of the droplet at the point where the curved surface of the droplet intersects the solid surface. A tangent line is taken and the angle is measured (tangent method). In this specification, a contact angle meter CA-DT manufactured by Kyowa Interface Science Co., Ltd. was used as the contact angle meter.

  In this specification, in order to distinguish the contact angle between the body fluid component adhesion preventing layer and the binder resin, the contact angle of the body fluid component adhesion preventing layer is referred to as “contact angle of the body fluid component adhesion preventing layer” or simply “contact angle”. The contact angle of the binder resin is referred to as “the contact angle of the binder resin”.

  In view of the above points among the binder resins, acrylic silicone resins, fluororesins, and acrylic urethane resins, which are copolymers of acrylic monomers and silyl group-containing polymerizable monomers, are more preferred, acrylic silicone resins Fluorine resin is particularly preferable. In addition, the said binder resin may be used independently or may be used with the form of 2 or more types of mixtures.

  When the intermediate layer contains a binder resin, the amount of the binder resin used is not particularly limited as long as it is an amount that can satisfactorily hold the hydrophobic fine particles. Specifically, the binder resin can be mixed with the hydrophobic fine particles in a ratio of preferably 100 to 100,000 parts by weight, more preferably 250 to 10,000 parts by weight with respect to 100 parts by weight of the hydrophobic fine particles. With such an amount, the hydrophobic fine particles can be satisfactorily retained in the intermediate layer (body fluid component adhesion preventing layer), so that an excellent body fluid component adhesion preventing effect, water repellency, durability and the like can be achieved.

  Moreover, when an intermediate | middle layer contains binder resin, it is preferable that a crosslinking agent is further included. Since the film strength is increased by reaction with the binder resin (crosslinking reaction), more excellent durability (particularly durability against friction) can be achieved. Here, it does not restrict | limit especially as a crosslinking agent, According to the kind of binder resin used, it can select suitably. Specific examples include usual crosslinking agents such as isocyanate and carbodiimide. Among these, although it does not restrict | limit especially as an isocyanate type crosslinking agent, Triallyl isocyanate, dimer acid diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6- TDI), 4,4′-diphenylmethane diisocyanate (4,4′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetra Aromatic diisocyanates such as methylxylidene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI); hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate Aliphatic diisocyanates such as lysate (TMHDI), lysine diisocyanate, norbornane diisocyanate methyl (NBDI); transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H6-XDI (hydrogenated XDI), H12- Examples thereof include alicyclic diisocyanates such as MDI (hydrogenated MDI); carbodiimide-modified diisocyanates of the above diisocyanates; or their isocyanurate-modified diisocyanates. Moreover, the adduct body of said isocyanate compound and polyol compounds, such as a trimethylol propane, the biuret body and isocyanurate body of these isocyanate compounds can also be used conveniently. In addition, an isocyanate type crosslinking agent may be synthesize | combined and a commercial item may be used. Examples of commercially available products include Coronate (registered trademark) L, Coronate (registered trademark) HL, Coronate (registered trademark) 2030, Coronate (registered trademark) 2031 (manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate (registered trademark). D-102, Takenate (registered trademark) D-110N, Takenate (registered trademark) D-200, Takenate (registered trademark) D-202 (manufactured by Mitsui Chemicals, Inc.), Duranate (trademark) 24A-100, Duranate ( (Trademark) TPA-100, Duranate (trademark) TKA-100, Duranate (trademark) P301-75E, Duranate (trademark) E402-90T, Duranate (trademark) E405-80T, Duranate (trademark) TSE-100, Duranate (trademark) D-101, Duranate (trademark) D-20 (Above, manufactured by Asahi Kasei Chemicals Co., Ltd.), and the like. The said isocyanate type crosslinking agent may be used independently and may be used in combination of 2 or more type.

  The carbodiimide-based crosslinking agent is not particularly limited, but a compound having two or more carbodiimide groups (—N═C═N—) in the molecule is preferably used, and a known polycarbodiimide can be used. Moreover, as a carbodiimide compound, the high molecular weight polycarbodiimide produced | generated by carrying out the decarboxylation condensation reaction of diisocyanate in presence of a carbodiimidization catalyst can also be used. Examples of such compounds include those obtained by subjecting the following diisocyanates to a decarboxylation condensation reaction. As the diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 3,3′-dimethyl-4,4′-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4′- One of dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, or a mixture of two or more thereof can be used. As the carbodiimidization catalyst, 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl- Phosphorene oxides such as 2-phospholene-1-oxide or their 3-phospholene isomers can be used. The carbodiimide-based crosslinking agent may be synthesized or a commercially available product may be used. Examples of commercially available products include Carbodilite (registered trademark) series manufactured by Nisshinbo Chemical Co., Ltd. Among these, Carbodilite (registered trademark) V-01, V-03, V-05, V-07, and V-09 are preferable because of excellent compatibility with organic solvents. The said carbodiimide type crosslinking agent may be used independently, and may be used in combination of 2 or more type.

  The amount of the crosslinking agent used is not particularly limited as long as it is an amount capable of appropriately crosslinking the binder resin, but is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the binder resin. If it is this range, an intermediate | middle layer (body fluid component adhesion prevention layer) will exhibit high intensity | strength, and may have the outstanding durability.

  In place of the binder resin or in addition to the binder resin, when the intermediate layer, particularly the intermediate layer contains hydrophobic fine particles, the body fluid component adhesion preventing layer has the ability to retain hydrophobic fine particles, adhesion to a transparent substrate, etc. In view of the above, it is preferable to include a metal alkoxide. Metal alkoxide interacts with hydrophobic fine particles. That is, for example, when the hydrophobic fine particles are hydrophobic silica fine particles and the metal alkoxide is tetraalkoxysilane, the hydrophobic fine particles and the metal alkoxide are bonded via a silanol bond (—Si—O—Si—). Join. For this reason, even if the surface of the transparent structure is in contact with a biological tissue (for example, the inner wall of a lumen), the hydrophobic fine particles are firmly held in the body fluid component adhesion preventing layer via the metal alkoxide in the intermediate layer. Therefore, the body fluid component adhesion preventing effect, water repellency, durability and the like can be further improved.

The metal alkoxide is a compound represented by the formula: M (OX) _p . Here, M represents silicon (Si), titanium (Ti), aluminum (Al), zinc (Zn), or zirconium (Zr). Of these, silicon, aluminum, zinc and zirconium are preferable, and silicon is particularly preferable. X is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Specific examples of the linear, branched or cyclic alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and isopentyl. , Neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Of these, a linear or branched alkyl group having 1 to 3 carbon atoms is preferable. When a plurality of X exist (that is, p is an integer of 2 or more), each X may be the same or different. Furthermore, p is an integer indicating the valence of the element M, and is uniquely defined by the type of M. Specifically, the metal alkoxide is not particularly limited, but includes tetramethoxysilane [Si (OCH ₃ ) ₄ ], tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ], tetraisopropoxysilane [Si (OCH ( CH _{3) 2) 4],} tetrabutoxysilane, triisopropoxyaluminum _{[Al (OCH (CH 3)} 2) 3], zirconium -n- butoxide _{[Zr (OC 4 H 9)} 3], zinc tetraethoxide [ Zn (OCH ₃ ) ₄ ] and the like.

  When the intermediate layer contains a metal alkoxide, the amount of the metal alkoxide used is not particularly limited as long as it can interact with the hydrophobic fine particles satisfactorily. Specifically, the metal alkoxide can be mixed with the hydrophobic fine particles in a ratio of preferably 5,000 to 1,000,000 parts by weight, more preferably 1,000 to 100,000 parts by weight with respect to 100 parts by weight of the hydrophobic fine particles. With such an amount, the hydrophobic fine particles and the metal alkoxide can interact well in the intermediate layer (body fluid component adhesion preventing layer), thus achieving excellent body fluid component adhesion prevention, water repellency, durability, etc. it can.

  Moreover, when the intermediate layer contains both the binder resin and the metal alkoxide, the amount of each of the binder resin and the metal alkoxide is sufficient as long as it is within the above range, and the mixing ratio thereof is not particularly limited. Preferably, the metal alkoxide is mixed in an amount of 50 to 200 parts by weight, more preferably 100 to 150 parts by weight, with respect to 100 parts by weight of the binder resin.

[Method for producing transparent structure]
Although the manufacturing method of the transparent structure of the present invention is not particularly limited as long as it has the structure as described above, it is preferable to manufacture the transparent structure by any of the following methods (1) to (6). .
(1) After the surface of the transparent substrate is softened, hydrophobic fine particles are disposed on the softened surface;
(2) After the surface of the transparent substrate is softened and hydrophobic fine particles are arranged on the softened surface to form a body fluid component adhesion preventing layer, the surface of the body fluid component adhesion preventing layer is spaced 600 μm or less in width, 200 μm or less in width, and deep. Forming a groove having a thickness of 50 μm or less;
(3) A transparent base material having an intermediate layer is prepared, and hydrophobic fine particles are arranged on the surface of the intermediate layer;
(4) A transparent base material having an intermediate layer is prepared, and after forming grooves having a spacing of 600 μm or less, a width of 200 μm or less, and a depth of 50 μm or less on the surface of the intermediate layer, hydrophobic fine particles are disposed on the groove forming surface;
(5) A transparent base material having an intermediate layer is prepared, and hydrophobic body particles are arranged on the surface of the base material to form a body fluid component adhesion preventing layer. Then, the surface of the body fluid component adhesion preventing layer has a spacing of 600 μm or less and a width of 200 μm. Or a groove having a depth of 50 μm or less; or (6) forming a groove having a spacing of 600 μm or less, a width of 200 μm or less and a depth of 50 μm or less on the transparent substrate surface; Hydrophobic fine particles are arranged on the groove forming surface.

  Hereinafter, although the said preferable manufacturing method (1)-(6) is explained in full detail, this invention is not limited to the following form.

(Softening treatment of transparent substrate surface)
By softening the transparent substrate, the intermediate layer placed on the substrate surface is mixed with the substrate layer, or the hydrophobic fine particles placed on the substrate surface are partially embedded in the substrate, preventing body fluid adhesion The durability of the layer can be improved. Here, the method of softening the substrate is not particularly limited, and can be appropriately selected depending on the material of the transparent substrate used. For example, a method of immersing a transparent substrate in a softening solvent can be used. Here, the softening solvent is not particularly limited, and can be appropriately selected depending on the material of the transparent substrate to be used. For example, when the transparent substrate is a PMMA substrate, butyl acetate, acetone, dichloromethane or the like can be used as the softening solvent. These may be used alone or may be used by arbitrarily mixing with other solvents.

Moreover, the softening process conditions of a transparent base material will not be restrict | limited especially if the base-material surface can be softened. Considering the effect of improving the durability of the body fluid adhesion preventing layer as described above, it is preferable that the reduced weight of the transparent base material after the softening treatment is in a condition of 0.001 to 15 mg / cm ^2. More preferably, the condition is 1 to 10 mg / cm ² .

(Formation of intermediate layer)
The intermediate layer preferably contains a binder resin and, if necessary, at least one of a crosslinking agent and a metal alkoxide. The method for forming the intermediate layer is not particularly limited, and known methods can be applied in the same manner or appropriately modified. Specifically, (a) a binder resin and a crosslinking agent are added to a suitable solvent; (b) a binder resin and a metal alkoxide are added to a suitable solvent; (c) a binder resin, a crosslinking agent and a metal alkoxide. Is added to a suitable solvent; a coating agent is prepared, this coating agent is applied to the softened substrate surface, and heat-treated if necessary to form an intermediate layer. In this method, the appropriate solvent is not particularly limited as long as it can dissolve or disperse each component appropriately. Specifically, alcohols such as methanol, ethanol, propanol, isopropanol and ethylene glycol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, halides such as chloroform, olefins such as hexane, tetrahydrofuran (THF ), Ethers such as butyl ether, aromatics such as benzene and toluene, amides such as N, N-dimethylformamide (DMF), and the like. Here, the addition amount of each component in the solution is not particularly limited. In (a), the amount of the binder resin added is not particularly limited as long as the amount of the binder resin is mixed with the hydrophobic fine particles, but the binder resin: solvent mixing ratio (weight ratio) ) Is preferably 5: 100 to 50: 100. In addition, in (b), the amount of metal alkoxide added is not particularly limited as long as the amount of metal alkoxide is mixed with hydrophobic fine particles, but the metal alkoxide: solvent mixing ratio ( It is preferable that the weight ratio is 1:99 to 50:50. Further, in the above (c), the addition amount of the binder resin and the metal alkoxide is not particularly limited as long as the amount of the binder resin and the metal alkoxide is mixed with the hydrophobic fine particles. The total addition amount of the binder resin and the metal alkoxide: the solvent is preferably mixed in an amount (weight ratio) of 1:99 to 50:50. In addition, in the above (a) and (c), when the binder resin is used in combination with a crosslinking agent, the addition amount of the crosslinking agent may be an amount that can be a mixing ratio with the binder resin as described above. .

  The method for applying the coating agent to the softened substrate surface is not particularly limited. For example, spray coating (spraying method), dip coating (dipping method), spin coating, bar coating, roll coating, screen printing, etc. Can be used. After coating, the coating film may be used as it is in the subsequent hydrophobic particle placement step (formation of body fluid component adhesion preventing layer), but if necessary, the coating film may be appropriately dried before the above step. Good.

(Groove formation)
The method for forming the groove is not particularly limited. Specifically, a method in which a mesh, a stamp, a needle, or the like is placed on the intermediate layer or the body fluid component adhesion preventing layer and hot-pressed can be used. These materials are not particularly limited, but preferably have heat resistance when performing hot pressing. Specifically, metals such as copper, stainless steel, iron, platinum, and gold, and resins such as nylon and polyimide can be used.

  The hot press conditions are not particularly limited as long as the predetermined groove portions can be formed in the intermediate layer or the body fluid component adhesion preventing layer. For example, the hot pressing temperature is preferably from room temperature to the base material deformation temperature, more preferably 40 to 140 ° C, and particularly preferably 50 to 100 ° C. The hot press pressure is preferably 0.1 to 30 MPa, more preferably 1 to 20 MPa, and particularly preferably 5 to 15 MPa. The hot pressing time is preferably 1 to 30 minutes, and more preferably 3 to 10 minutes.

(Disposition of hydrophobic fine particles)
The method for arranging the hydrophobic fine particles (formation of the body fluid component adhesion preventing layer) is not particularly limited. For example, a dispersion solution of the hydrophobic fine particles may be spray coated (dip method), dip coat (dipping method), spin coat, bar A method of drying and heating after coating on the surface of the substrate by a method such as coating, roll coating or screen printing can be used. Here, the solvent for dispersing the hydrophobic fine particles is not particularly limited, but alcohols such as methanol, ethanol, propanol, isopropanol and ethylene glycol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, chloroform and the like Halides, olefins such as hexane, ethers such as tetrahydrofuran (THF) and butyl ether, aromatics such as benzene and toluene, amides such as N, N-dimethylformamide (DMF), and the like. The dispersion amount of the hydrophobic fine particles in the solution is not particularly limited as long as a sufficient amount of the hydrophobic fine particles can be disposed on the surface of the substrate, and depends on the softening conditions of the substrate surface, the type and particle size of the hydrophobic fine particles, and the like. Are appropriately selected. Specifically, the hydrophobic fine particles are dispersed in the solvent so as to have a concentration of preferably 0.05 to 20% by weight, more preferably 1 to 9% by weight.

After the hydrophobic fine particles are coated on the surface of the transparent substrate, the transparent substrate is dried and heated. As a result, a body fluid component adhesion preventing layer composed of hydrophobic fine particles is formed on the transparent substrate. Here, the arrangement amount (application amount) of the hydrophobic fine particles on the transparent substrate surface is not particularly limited. Considering film strength, hydrophobic fine particle retention, body fluid component adhesion preventing effect, water repellency, durability, etc., 0.005 to 20 mg / cm ² is preferable, and 0.01 to 10 mg / cm ² . Is more preferable, and 0.5 to 5 mg / cm ² is particularly preferable. The drying / heating conditions are not particularly limited, and may be set as appropriate depending on the heat resistance of the base material, the type of solvent, and the like. Specifically, the drying / heating temperature is preferably in the range of not less than the volatilization temperature of the solvent and not more than 300 ° C. The drying / heating time is not particularly limited as long as the hydrophobic fine particles can be fixed to the surface of the substrate, but is preferably 0.5 to 24 hours, and more preferably 1 to 10 hours.

  The order of the hydrophobic fine particle arranging step and the groove forming step may be either the hydrophobic fine particle arranging step after the groove forming step or the groove forming step after the hydrophobic fine particle arranging step. In the former case, a groove portion having a desired shape can be formed more accurately, and hydrophobic fine particles can be selectively disposed in the groove portion. In the latter case, hydrophobic fine particles can be held both on and in the body fluid component adhesion preventing layer (or intermediate layer).

  Among the above methods, the methods (2), (3), (4) and (6) are preferable, and the methods (4) and (6) are more preferable.

[Transparent structure]
Since the transparent structure of the present invention is transparent, for example, when applied to the lens surface of an endoscope, sufficient visibility can be ensured. Here, the transparent structure is not particularly limited as long as it exhibits visible light transmittance that can achieve sufficient visibility, but the transparent structure is preferably 60% or more, more preferably 70% or more, and particularly preferably. Has a visible light transmittance of 80% or more (upper limit: 100%).

  Moreover, the transparent structure of the present invention is excellent in ability to prevent adhesion of body fluid components and water repellency. Here, the “body fluid component adhesion preventing ability” or “body fluid component adhesion preventing effect” means that a body fluid component (mucus, blood, etc.) derived from a living body is difficult to adhere to the transparent structure. In the present specification, the “body fluid component adhesion preventing ability” or “body fluid component adhesion preventing effect” can also be defined by the amount of albumin adsorbed on the surface of the transparent structure. Specifically, the transparent structure having the body fluid component adhesion preventing layer of the present invention is a transparent base material in which the albumin adsorption amount on the surface of the crystal resonator microbalance (QCM) does not form the body fluid component adhesion preventing layer. Is preferably 1/5 or less, more preferably 1/10 or less, and particularly preferably 1/100 or less (lower limit: 0). Such an albumin adsorption amount can be achieved by a contact angle of 150 degrees or more by the transparent structure of the present invention, particularly by a contact angle of 150 degrees or more and a falling angle of 20 degrees or less by the transparent structure of the present invention. Here, the “albumin adsorption amount on the electrode surface of the quartz crystal microbalance (QCM)” is obtained from the frequency change (Frequency Shift) (Hz) measured by the following method. That is, the relationship between the amount of change in frequency and the amount of adhering substance is expressed by the Sauerbrey equation. When the amount of adhering substance increases, the frequency decreases, and when the amount of adhering substance decreases, the frequency increases. Utilizing this phenomenon, the crystal resonator formed with a transparent structure is immersed in an albumin aqueous solution, and the change in mass of the substance on the crystal resonator (electrode) is detected by detecting the frequency change amount (ie, Albumin absorption amount) can be calculated. In the method described below, a frequency decrease of 1 Hz (-1 Hz) corresponds to about 1 ng of albumin adhering to the transparent structure formed on the crystal resonator (electrode).

(Measurement method of albumin adsorption on the electrode surface of quartz crystal microbalance (QCM))
After hydrophilizing the quartz crystal microbalance (QCM) electrode with a 1 wt% potassium hydroxide solution, a transparent substrate (transparent substrate layer) and a body fluid adhesion preventing layer are formed on the QCM electrode by dip coating. The QCM electrode on which the transparent substrate and the body fluid adhesion preventing layer are formed is immersed in phosphate buffered saline (PBS) for 1 hour to stabilize the frequency, and then immersed in an albumin aqueous solution (BSA solution) adjusted to 50 μM for 1 hour. . Measure the frequency change (Hz) between the frequency (Hz) immediately immersed in the albumin aqueous solution and the frequency (Hz) one hour after immersion in the albumin aqueous solution, and calculate the mass change equivalent to the frequency change amount. It is defined as albumin adsorption amount (albumin adsorption amount of the body fluid component adhesion preventing layer). Similarly, only a transparent substrate (transparent substrate layer) is formed on the QCM electrode, and the amount of albumin adsorbed is measured, and this is used as the amount of albumin adsorbed on the transparent substrate. Both values are compared, and the ratio of the albumin adsorption amount of the body fluid component adhesion preventing layer to the albumin adsorption amount of the transparent substrate is calculated.

  “Water repellency” is expressed as a contact angle with water, and when the contact angle with water is large, it is referred to as having water repellency. Alternatively, “water repellency” may be expressed by a contact angle and a falling angle with respect to water, and in this case, when the contact angle with respect to water is large and the falling angle is low, it is referred to as having water repellency. Specifically, the body fluid component adhesion preventing layer of the transparent structure of the present invention can exhibit super water repellency with a water contact angle of 150 ° or more, preferably a water contact angle of 150 ° or more and a falling angle. Super water repellency of 20 degrees or less can be exhibited. More preferably, the body fluid component adhesion preventing layer of the transparent structure of the present invention exhibits super water repellency with a water contact angle of 150 ° or more and a falling angle of 10 ° or less. Here, the “contact angle with water” can be measured in the same manner as the contact angle of the binder resin. Also, the “falling angle” is defined as the angle of the solid plate when the droplet placed on the solid plate starts to fall, and the stage on which the solid plate with which the droplet is contacted is tilted to drop the droplet. The stage can be stopped when it falls and the angle can be measured.

[Endoscope]
As described above, the transparent structure of the present invention can exhibit excellent body fluid component adhesion prevention and water repellency, and therefore can be suitably used as a lens cover on the lens surface of an endoscope. Therefore, the present invention is an endoscope having an optical element for observing a region to be examined at the distal end, and also includes an endoscope in which the transparent structure of the present invention is provided on the surface of the optical element. provide. According to the present invention, it is possible to effectively suppress and prevent the attachment of body fluid components (mucus, blood, etc.) derived from a living body without a washing operation, and to ensure good visibility through an endoscope lens.

  Here, the transparent structure of the present invention can be applied as a lens cover of any endoscope. That is, the endoscope of the present invention is characterized in that the transparent structure of the present invention is installed as a lens cover on the lens surface, and there is no characteristic in the structure of the other endoscopes. A preferred embodiment thereof is shown in FIG. 15 below, but the present invention is not limited to this embodiment.

  FIG. 15 is an enlarged cross-sectional view showing an outline of the configuration of the distal end portion of the endoscope according to a preferred aspect of the present invention. In FIG. 15, at the distal end of the endoscope 100 of the present invention, the transparent structure of the present invention is used as the lens cover 102 of the distal end (distal end) of the objective lens 101 or the distal end (distal end) of the illumination lens 103. The lens cover 104 can be installed. As a result, body fluid components (mucus, blood, etc.) derived from a living body are not or hardly adhered to the surface of these lens covers even without a washing operation, so that the inside of the living body can be viewed well through the endoscope lens. In FIG. 15, the air / liquid supply nozzle 105 is installed at the endoscope tip, but as described above, according to the endoscope of the present invention, there is no cleaning operation by the air / liquid supply nozzle. However, since sufficient visibility can be secured, the air / liquid feeding nozzle 105 can be omitted. Further, when the air / liquid feeding nozzle 105 is installed, the cleaning liquid sprayed from the nozzle does not adhere to the lens cover surface or hardly due to the water repellency of the transparent structure of the present invention. For this reason, even in such a case, by using the transparent structure of the present invention as a lens cover, the inside of the living body can be favorably visually recognized through the endoscope lens.

  Moreover, in this invention, you may provide a recessed part in the front-end | tip (distal end) of a transparent structure. That is, it is preferable that the transparent structure of the present invention has a recess recessed from the surface of the body fluid component adhesion preventing layer. By using the concave lens cover in this way, the concave portion can be a space for air accumulation when in contact with the liquid. For this reason, even when the endoscope is immersed in body fluid, an air layer is formed at the distal end (distal end) of the endoscope, and this air layer suppresses contact with body fluid components derived from living bodies. ·To prevent. For this reason, by taking the said structure, since a contact with the bodily fluid component derived from a biological body can be suppressed / prevented more effectively, the tip part becomes less likely to be contaminated, and better visibility can be achieved. Here, the concave shape is not particularly limited. For example, the transparent structure 1 having a structure in which both the transparent base material 2 and the body fluid component adhesion preventing layer 5 are recessed in a rectangular shape is installed at the tip of the lens 10. Form (FIG. 14A); Form in which transparent structure 1 having a structure in which both transparent substrate 2 and body fluid component adhesion preventing layer 5 are recessed in an inverted trapezoidal shape is installed at the tip of lens 10 (FIG. 14B); A transparent structure 1 having a structure in which only the prevention layer 5 is recessed in a rectangular shape (FIG. 14C); and a transparent structure in which only the body fluid component adhesion prevention layer 5 is recessed in an inverted trapezoidal shape. The structure (FIG. 14D) etc. with which the structure 1 is installed in the front-end | tip of the lens 10 are mentioned.

  The transparent structure formed by disposing a body fluid component adhesion preventing layer having hydrophobic fine particles on at least a part of the surface of the transparent substrate of the present invention is transparent in addition to the lens surface lens cover of the endoscope described above. And can be used as appropriate for members that can come into contact with body fluids. Specifically, the transparent structure of the present invention, various body cavities such as a feeding catheter, aspiration catheter, and urinary catheter, organs, catheters and tubes inserted or placed in tissues, blood bags and transfusion tubes, extracorporeal It can also be applied to medical devices for circulatory treatment (artificial lung, artificial heart, artificial kidney, etc.), circuits thereof, collection devices and analysis devices for collecting and analyzing body fluid components, and the like.

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples.

Example 1
A PMMA substrate (thickness: 0.2 mm) as a transparent substrate was dipped in a 30% by volume dichloromethane solution mixed with ethanol to soften the substrate surface. In addition, the said softening process was performed so that the weight of a PMMA base material might reduce 0.3 mg / cm < ² >. After immersing the PMMA substrate whose surface was softened in this way in a mixed solution of tetraethoxysilane and ethanol as a metal alkoxide (tetraethoxysilane: ethanol mixture ratio = 7: 93 (weight ratio)), Raised. Under the present circumstances, immersion was performed so that the arrangement amount (application amount) of a metal alkoxide might be 0.16 mg / cm < ² >. Next, the PMMA substrate coated with tetraethoxysilane was dipped in a 4 wt% hydrophobic silica ethanol dispersion and then pulled up. At this time, the immersion was performed so that the amount of the hydrophobic silica fine particles disposed (application amount) was 0.65 mg / cm ² . The PMMA substrate coated with the hydrophobic silica fine particles was heated at 140 ° C. for 1 hour to form a body fluid component adhesion preventing layer containing the hydrophobic silica fine particles and tetraethoxysilane on the PMMA substrate. As the hydrophobic silica fine particles used in this example, AEROSIL (registered trademark) RX200 manufactured by Nippon Aerosil Co., Ltd. (average particle diameter (average particle diameter (diameter) of primary particles): 12 nm, surface-treated with a trimethylsilyl group. Silica particles) (hereinafter also referred to as “hydrophobic silica fine particles RX200”).

  Further, a Cu mesh was placed on the PMMA base material on which the body fluid component adhesion preventing layer was formed, and hot-pressed at a temperature of 100 ° C. and a pressure of 10 MPa for 3 minutes. As a result, grooves having an interval of 400 μm, a width of 100 μm, and a depth of 10 μm were formed on the surface of the body fluid component adhesion preventing layer. What was obtained in the present Example is called a transparent structure (1).

  The body fluid component adhesion preventing layer of the transparent structure (1) exhibited super water repellency with a water contact angle of 150 ° or more and a falling angle of 10 ° or less. Moreover, this transparent structure (1) was observed with SEM and a laser microscope, and the result is shown to FIG. 3A and FIG. 3B, respectively. From FIG. 3, it can be seen that on the surface of the transparent structure (1) of the present invention, numerous fine uneven structures are formed by hydrophobic fine particles, and grooves are formed by Cu mesh. Moreover, when the cross section of the transparent structure (1) was observed, as shown in FIG. 1E, the hydrophobic silica fine particles were partially exposed from the surface of the body fluid component adhesion preventing layer (including the groove portion) and partly exposed. It was observed that the body fluid component adhesion preventing layer was formed in a state of being embedded in the body fluid component adhesion preventing layer (including the groove). With respect to the transparent structure (1), the visible light transmittance and blood contamination preventing ability were evaluated according to the following methods. As a result, the visible light transmittance of the transparent structure (1) was 90%, and it was found that the transparent structure (1) had high transparency. In addition, as shown in FIG. 4, in the transparent structure (1), blood adhesion was recognized in part, but blood adhesion was suppressed in most regions.

<Measurement of visible light transmittance>
About each transparent structure, the transmittance | permeability in a 400-800 nm wavelength range was measured, and the average value was made into the visible light transmittance | permeability.

<Evaluation of ability to prevent blood contamination>
Each transparent structure was immersed in human whole blood (heparin addition amount: 0.75 unit / mL) for 1 minute, and the appearance after removal was observed with the naked eye.

Example 2
An acrylic silicone resin (My Block Wako 101, manufactured by Wako Pure Chemical Industries, Ltd.) as a binder resin and tetraethoxysilane as a metal alkoxide are mixed in a ratio of 50:50 (= acrylic silicone resin: tetraethoxysilane weight ratio). The mixture was diluted 5 times with ethanol to prepare a coating agent. In addition, about the acrylic silicone resin used by the present Example, the contact angle of binder resin was 90 degree | times. In this coating agent, a PMMA substrate (thickness: 2 mm) as a transparent substrate was dipped and then pulled up. In addition, the immersion was performed so that the amount (application amount) of the binder resin was 1.5 mg / cm ² . Next, the PMMA base material coated with the coating agent was heated at 80 ° C. for 2 hours to form an intermediate layer on the surface of the base material.

  A nylon mesh was placed on the PMMA base material on which the intermediate layer was formed in this way, and hot pressed at a temperature of 80 ° C. and a pressure of 10 MPa for 5 minutes. As a result, grooves having a spacing of 170 μm, a width of 90 μm, and a depth of 18 μm were formed on the surface of the body fluid component adhesion preventing layer.

Thus, the PMMA base material in which the groove part was formed in the intermediate | middle layer was pulled up, after being immersed in the hydrophobic silica ethanol dispersion liquid similar to Example 1. FIG. By heating this PMMA base material at 80 ° C. for 1 hour, a body fluid component adhesion preventing layer containing hydrophobic silica fine particles RX200, an acrylic silicone resin and tetraethoxysilane was formed on the PMMA base material. At this time, the immersion was performed so that the amount of the hydrophobic silica fine particles disposed (coating amount) was 0.68 mg / cm ² . What was obtained in the present Example is called a transparent structure (2).

  The body fluid component adhesion preventing layer of the transparent structure (2) exhibited super water repellency with a water contact angle of 150 ° or more and a falling angle of 10 ° or less. Moreover, this transparent structure (2) was observed with SEM and a laser microscope, and the result is shown to FIG. 5A and FIG. 5B, respectively. From FIG. 5, it can be seen that on the surface of the transparent structure (2) of the present invention, numerous fine uneven structures are formed by hydrophobic fine particles, and grooves are formed by nylon mesh. Moreover, when the cross section of the transparent structure (2) was observed, as shown in FIG. 2H, hydrophobic silica fine particles were partially exposed from the surface of the body fluid component adhesion preventing layer (including the groove portion) and partly exposed. It was observed that it was embedded in the body fluid component adhesion preventing layer (including the groove). Furthermore, with respect to the transparent structure (2), the visible light transmittance and the blood contamination preventing ability were evaluated in the same manner as in Example 1. As a result, the visible light transmittance of the transparent structure (2) was 80%. Further, as shown in FIG. 6, the transparent structure (2) showed no blood adhesion over the entire surface.

Example 3
A coating agent was prepared by mixing 20 parts by weight of 4,4′-diphenylmethane diisocyanate as an isocyanate-based crosslinking agent with 100 parts by weight of the acrylic silicone resin similar to Example 2, and diluting with the same amount of butyl acetate as this mixture. did. In this coating agent, a PMMA substrate (thickness: 2 mm) as a transparent substrate was dipped and then pulled up. Next, the PMMA substrate coated with the coating agent was dried at room temperature for 12 hours to form an intermediate layer on the substrate surface. At this time, the immersion was performed so that the film forming amount of the intermediate layer was 0.68 mg / cm ² .

Thus, the PMMA base material in which the intermediate layer was formed on the surface was immersed in the same hydrophobic silica ethanol dispersion as in Example 1 and then pulled up. By heating this PMMA base material at 80 ° C. for 5 hours, a body fluid component adhesion preventing layer containing hydrophobic silica fine particles RX200 and an acrylic silicone resin was formed on the PMMA base material. At this time, the immersion was performed so that the amount of the hydrophobic silica fine particles disposed (application amount) was 0.82 mg / cm ² . What was obtained in the present Example is called a transparent structure (3).

  The body fluid component adhesion preventing layer of the transparent structure (3) exhibited super water repellency with a water contact angle of 150 ° or more and a falling angle of 10 ° or less. Moreover, this transparent structure (3) was observed with SEM and a laser microscope, and the result is shown to FIG. 7A and FIG. 7B, respectively. From FIG. 7, it can be seen that a large number of fine uneven structures are formed by hydrophobic fine particles on the surface of the transparent structure (3) of the present invention. Further, when the cross section of the transparent structure (3) was observed, hydrophobic silica fine particles were partially exposed from the body fluid component adhesion preventing layer surface and partly exposed to the body fluid component adhesion preventing layer, as shown in FIG. 1C. It was observed that it was buried inside. Further, with respect to the transparent structure (3), the visible light transmittance and the blood contamination preventing ability were evaluated in the same manner as in Example 1. As a result, the visible light transmittance of the transparent structure (3) was 86%. Further, as shown in FIG. 8, the transparent structure (3) showed no blood adhesion over the entire surface.

Example 4
A nylon mesh was placed on a PMMA substrate (thickness: 0.2 mm) as a transparent substrate, and hot pressed at a temperature of 100 ° C. and a pressure of 15 MPa for 10 minutes. As a result, grooves having an interval of 40 μm, a width of 25 μm, and a depth of 8 μm were formed on the surface of the PMMA substrate. Immediately after hot pressing, the PMMA substrate was dipped in the same hydrophobic silica ethanol dispersion as in Example 1 and then pulled up. The PMMA base material was heated at 80 ° C. for 1 hour to form a body fluid component adhesion preventing layer composed of hydrophobic silica fine particles RX200 on the PMMA base material. At this time, the immersion was performed so that the amount of the hydrophobic silica fine particles disposed (application amount) was 0.64 mg / cm ² . What was obtained in the present Example is called a transparent structure (4).

  The body fluid component adhesion preventing layer of the transparent structure (4) exhibited super water repellency with a water contact angle of 150 ° or more and a falling angle of 10 ° or less. Moreover, this transparent structure (4) was observed with SEM and a laser microscope, and the result is shown to FIG. 9A and FIG. 9B, respectively. From FIG. 9, it can be seen that a large number of fine uneven structures are formed by hydrophobic fine particles on the surface of the transparent structure (4) of the present invention. Moreover, when the cross section of the transparent structure (4) was observed, as shown in FIG. 1D, a part of the hydrophobic silica fine particles was exposed from the surface of the base material (including the groove), and a part of the base material ( It was observed that it was buried in (including the groove). Furthermore, with respect to the transparent structure (4), the visible light transmittance and blood contamination preventing ability were evaluated in the same manner as in Example 1. As a result, the visible light transmittance of the transparent structure (4) was 68%. Moreover, as shown in FIG. 10, the transparent structure (4) showed no adhesion of blood except for a part of the surface.

Example 5
20 parts by weight of the same isocyanate crosslinking agent as in Example 3 was mixed with 100 parts by weight of the same acrylic silicone resin as in Example 2, and diluted with the same amount of butyl acetate as this mixture to prepare a coating agent. In this coating agent, a PMMA substrate (thickness: 0.2 mm) as a transparent substrate was dipped and then pulled up. Next, the PMMA substrate coated with the coating agent was dried at room temperature for 12 hours to form an intermediate layer on the substrate surface. At this time, the immersion was performed so that the film forming amount of the intermediate layer was 0.67 mg / cm ² .

Thus, the SUS mesh was mounted on the PMMA base material having the intermediate layer formed on the surface, and hot pressing was performed at a temperature of 100 ° C. and a pressure of 15 MPa for 3 minutes. As a result, grooves having a spacing of 40 μm, a width of 25 μm, and a depth of 13 μm were formed on the intermediate layer surface. Next, the PMMA substrate was dipped in the same hydrophobic silica ethanol dispersion as in Example 1 and then pulled up. The PMMA base material was heated at 80 ° C. for 1 hour to form a body fluid component adhesion preventing layer composed of hydrophobic silica fine particles RX200 on the PMMA base material. At this time, the immersion was performed so that the amount of the hydrophobic silica fine particles disposed (application amount) was 0.82 mg / cm ² . What was obtained in this example is referred to as a transparent structure (5).

  The body fluid component adhesion preventing layer of the transparent structure (5) exhibited super water repellency with a water contact angle of 150 ° or more and a falling angle of 10 ° or less. Moreover, this transparent structure (5) was observed with SEM and a laser microscope, and the result is shown to FIG. 11A and FIG. 11B, respectively. From FIG. 11, it can be seen that on the surface of the transparent structure (5) of the present invention, numerous fine uneven structures are formed by hydrophobic fine particles, and grooves are formed by SUS mesh. Moreover, when the cross section of the transparent structure (5) was observed, as shown in FIG. 2H, hydrophobic silica fine particles were partially exposed from the body fluid component adhesion preventing layer surface (including the groove), and partly exposed. It was observed that it was embedded in the body fluid component adhesion preventing layer (including the groove). Furthermore, with respect to the transparent structure (5), the visible light transmittance and blood contamination preventing ability were evaluated in the same manner as in Example 1. As a result, the visible light transmittance of the transparent structure (5) was 70%. In addition, as shown in FIG. 12, the transparent structure (5) exhibited blood adhesion on a part of the surface, but blood adhesion was suppressed in the most area.

Example 6
A quartz resonator microbalance (QCM) electrode hydrophilized with a 5 wt% aqueous potassium hydroxide solution was immersed in a dichloromethane solution in which PMMA was dissolved to form a PMMA (transparent substrate) thin film on the QCM electrode. Then, after immersing in the same hydrophobic silica ethanol dispersion liquid as Example 1, it pulled up and produced the bodily fluid adhesion prevention layer on the transparent base material. At this time, the immersion was performed so that the amount of the hydrophobic silica fine particles disposed (application amount) was 0.82 mg / cm ² . The transparent structure created on the QCM electrode is referred to as a transparent structure (6). The QCM electrode was immersed in phosphate buffered saline for 1 hour to stabilize the frequency, and then immersed in an aqueous albumin solution (BSA solution) adjusted to 50 μM for 1 hour. The frequency change on the electrode surface immediately after immersion in the albumin aqueous solution was measured, and the change amount (frequency change amount) was calculated. Similarly, a QCM electrode on which only a PMMA thin film was formed was prepared, and the frequency change in an albumin aqueous solution was measured. The results are shown in FIG. In FIG. 13, the black circle (●) is the frequency variation of the QCM electrode (transparent structure (6)) having the body fluid adhesion preventing layer, and the white circle (◯) is the QCM having only the transparent substrate (PMMA thin film). This is the amount of change in the frequency of the electrode. As is clear from FIG. 13, the frequency change after 3600 seconds was 130 Hz in the QCM electrode having only the transparent structure, whereas the frequency change after 3600 seconds was 25 Hz in the transparent structure (6). That is, the albumin adsorption amount on the electrode surface of the quartz resonator microbalance (QCM) was reduced to 1/5 or less by forming the body fluid adhesion preventing layer. This result suggests that according to the transparent structure of the present invention, the adsorption of albumin can be significantly suppressed and prevented, and the suppression / prevention effect can be maintained over time.

Example 7
About the transparent structures (3) and (5) obtained in Examples 3 and 5 above, using a friction measuring machine (manufactured by Trinity Lab, Handy Tribomaster TL201) 20 shown in FIG. Sex was evaluated. That is, each transparent structure 21 was fixed in the petri dish 22 and immersed in pure water 23 having such a height that the entire transparent structure 21 was immersed. The petri dish 22 was placed on the moving table 24 of the friction measuring machine 20. A SUS R-shaped contactor (width 10 mm, R12 mm) 25 covered with gauze was brought into contact with the transparent structure 21, and a load 26 of 100 g was applied on the terminal 25. The moving table 24 was reciprocated horizontally 10 times at a speed of 5 mm / second and a moving distance of 10 mm, and the contact angle [degree] at the time of 0 times (before reciprocating movement), 5 times and 10 times reciprocating movement was measured. In addition, the resistance value at the time of rubbing in this evaluation was about 60 gf. The evaluation results are shown in FIG. As shown in FIG. 17, the transparent structure (3) having no groove part and the transparent structure (5) having the groove part formed in the body fluid component adhesion preventing layer are almost before the durability evaluation (0 reciprocation). Although the equivalent contact angle was shown, the transparent structure (5) in which the groove portion was formed in the body fluid component adhesion preventing layer was more rubbed (reciprocating) than the transparent structure (3) without the groove portion. It turns out that the fall of a contact angle can be suppressed. From this, it is considered that durability can be improved by forming a groove in the body fluid component adhesion preventing layer.

1 ... Transparent structure,
2 ... transparent substrate,
3 ... hydrophobic particles,
4 ... intermediate layer,
5 ... Body fluid component adhesion preventing layer,
6 ... Groove part.

Claims (7)

  A transparent structure comprising a body fluid component adhesion preventing layer having hydrophobic fine particles disposed on at least a part of a surface of a transparent substrate.   The transparent substrate or body fluid component adhesion preventing layer according to claim 1, wherein the transparent substrate or body fluid component adhesion preventing layer has grooves on the surface having a gap of 0.1 to 600 µm or less, a width of 0.1 to 200 µm or less, and a depth of 0.1 to 50 µm or less. Structure.   The said bodily fluid component adhesion prevention layer is a transparent structure of Claim 1 or 2 containing binder resin. The transparent structure according to any one of claims 1 to 3, wherein the transparent structure is produced by any one of the following methods (1) to (6):
(1) After the surface of the transparent substrate is softened, hydrophobic fine particles are disposed on the softened surface;
(2) After the surface of the transparent base material is softened and hydrophobic fine particles are arranged on the softened surface to form a body fluid component adhesion preventing layer, the surface of the body fluid component adhesion preventing layer has a spacing of 0.1 to 600 μm and a width of 0 Forming a groove of 1 to 200 μm and a depth of 0.1 to 50 μm;
(3) A transparent base material having an intermediate layer is prepared, and hydrophobic fine particles are arranged on the surface of the intermediate layer;
(4) A transparent base material having an intermediate layer is prepared, and after forming grooves with an interval of 0.1 to 600 μm, a width of 0.1 to 200 μm and a depth of 0.1 to 50 μm on the surface of the intermediate layer, the grooves are formed. Place hydrophobic particles on the surface;
(5) A transparent base material having an intermediate layer is prepared, and hydrophobic fine particles are arranged on the surface of the base material to form a body fluid component adhesion preventing layer, and then the surface of the body fluid component adhesion preventing layer is spaced 0.1 to 600 μm. Forming a groove having a width of 0.1 to 200 μm and a depth of 0.1 to 50 μm; or (6) a spacing interval of 0.1 to 600 μm, a width of 0.1 to 200 μm and a depth of 0.1 on the transparent substrate surface. After forming a groove of ˜50 μm, hydrophobic fine particles are disposed on the groove forming surface.   The transparent structure of any one of Claims 1-4 which has a recessed part dented from the said bodily fluid component adhesion prevention layer surface.   The body fluid component adhesion preventing layer has an albumin adsorption amount on an electrode surface of a crystal resonator microbalance (QCM) of 1/5 or less with respect to an albumin adsorption amount of the transparent substrate of the transparent substrate. 6. The transparent structure according to any one of 5 above.   An endoscope having an optical element for observing a region to be examined at the distal end, wherein the transparent structure according to any one of claims 1 to 6 is provided on a surface of the optical element. Endoscope.