WO2001060923A1 - Composition de resine permettant d'empecher la fixation d'organismes aquatiques ou de substances physiologiques - Google Patents

Composition de resine permettant d'empecher la fixation d'organismes aquatiques ou de substances physiologiques Download PDF

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Publication number
WO2001060923A1
WO2001060923A1 PCT/JP2001/001058 JP0101058W WO0160923A1 WO 2001060923 A1 WO2001060923 A1 WO 2001060923A1 JP 0101058 W JP0101058 W JP 0101058W WO 0160923 A1 WO0160923 A1 WO 0160923A1
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WIPO (PCT)
Prior art keywords
resin
water
same
och
adhesion
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PCT/JP2001/001058
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English (en)
Japanese (ja)
Inventor
Akira Chida
Kayoko Honda
Yasushi Yonei
Katsuhiko Imoto
Susumu Wada
Haruhiko Mohri
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Daikin Industries, Ltd.
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Priority to AU2001232295A priority Critical patent/AU2001232295A1/en
Publication of WO2001060923A1 publication Critical patent/WO2001060923A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds

Definitions

  • the present invention does not use chemicals that can be dissolved or released into the water, and can be used to aquatic or water-based products or structures.
  • the present invention relates to a technique for preventing the attachment of organisms, or preventing the attachment of cells or physiological substances to medical components, and easily removing even if attached. Background art
  • a hydrophobic fluororesin coating such as polytetrafluoroethylene (PTFE) is applied to the bottom of a ship, and the surface lubricity of the surface is used for aquatic organisms.
  • PTFE polytetrafluoroethylene
  • the dissolution of the metal poison is inevitable, which is not preferable because of the influence on the environment.
  • the method (3) also uses the reduction of the film thickness of the water-swellable resin, so it is necessary to consider the effect on the environment. Insufficient durability and stability.
  • the anti-adhesion effect for a long time is expected because these components are consumed. Can not .
  • the method (4) utilizes the characteristics of fluororesin, which is hydrophobic and has good surface lubricity, to reduce the resistance of a ship during traveling.
  • fluororesin which is hydrophobic and has good surface lubricity
  • a resin whose surface is mainly hydrophobic (a contact angle with water of 70 ° or more) (epoxy resin) is mainly used.
  • epoxy resin a resin whose surface is mainly hydrophobic (a contact angle with water of 70 ° or more)
  • Urethane resin, silicone resin, fluorine resin, curable acrylic resin, thermoplastic acrylic resin, polyester resin, alkyl resin, pheno resin Resin, melamine resin, urine resin, chlorinated rubber, etc. are used as film-forming components.
  • the purpose of the present invention is to provide a resin composition which does not release harmful components and prevents the attachment of aquatic substances or biological substances. .
  • Another purpose of the present invention is to prevent the release of harmful components into water, prevent aquatic organisms from adhering, and allow easy removal even if attached. To provide such structures.
  • Yet another object of the present invention is to provide a medical device to which cells and biological materials are not easily adhered and which can be easily removed even if adhered. It is in . Disclosure of the invention
  • the present invention relates to an aquatic organism or a biological substance containing a hydrolyzable organic metal compound (a) for surface hydrophilicity and a resin (b) for a binder.
  • the present invention relates to a resin composition for preventing adhesion of a substance.
  • the present invention relates to a product or structure used on a water surface having a surface on which a coating layer obtained from the resin composition is present or on the surface of water.
  • a coating layer obtained from the resin composition is present or on the surface of water.
  • the present invention provides a method for manufacturing a semiconductor device, comprising: a surface having a coating layer obtained from the resin composition; or a resin layer obtained from the resin composition. It relates to medical materials formed into shapes such as films, sheets or tubes.
  • the present invention provides a resin film having a coating layer obtained from the above resin composition on one surface of one of the resin films, and the other surface of the resin film.
  • a film that has an adhesive layer on the surface The present invention also relates to a marking film for use in an article or a structure or a medical member used in water or in water.
  • the present invention also provides a method of applying the resin composition to a surface of a product or a structure used on the surface of water or in water to form a coating film. How to prevent aquatic organisms from attaching to goods or structures, or
  • the present invention also relates to a method for preventing the attachment of physiological substances. Not only the best form for carrying out the invention, but also the aquatic organisms and physiological substances covered by the invention that are intended for use on the surface or in the water Structures and medical components that come into contact with physiological substances released from cells or living organisms are described.
  • structures include not only fixed structures such as piers and waterways, but also structures that mainly move such as ships.
  • Underwater structures such as piers, concrete blocks, wave-dissipating blocks, breakwaters, etc .;
  • Port facilities such as sluice gates, marine tanks and floating piers; Subsea operations such as undersea digging facilities and undersea communication cable facilities Facility;
  • Thermal power, atomic power, ocean thermal power generation facilities such as headraces, flood pipes, water chambers, etc .;
  • Fishery goods such as fishnets such as fixed nets, buoys, fish cages and ropes;
  • Thermal power such as water covers, water chambers, nuclear power, ocean thermal energy conversion materials;
  • Objects or structures used on the surface of the water or in the water will be contaminated with aquatic organisms and organic dirt, such as spikes, which will reduce their appearance and function. .
  • Floating oil mineral oil, vegetable oil, etc.
  • waste foods resins, human waste, dead creatures of living things, etc.
  • Medical components used directly on living bodies such as catheters, artificial blood vessels, artificial tissues, artificial bones, dialysis equipment, and various tubes;
  • Medical-related research and analysis equipment such as tissue, cell, and bacterial culture equipment, and physiological substance analysis equipment;
  • Cells also include unicellular organisms such as viruses and bacteria.
  • the resin composition of the present invention which can prevent the adhesion of these various organisms and substances, comprises a hydrolyzable organometallic compound (a) for surface hydrophilicity and a resin (b) for a binder. Including.
  • hydrolyzable organometallic compound (a) is present on the surface of a matrix (film or molded body) formed by the resin (b), and the hydrolyzable group is hydrolyzed. Makes the surface hydrophilic And acts to prevent the adhesion of the above-mentioned various organisms, physiological substances, and hydrophobic dirt. Therefore, such a hydrolyzable organometallic compound may be hereinafter referred to as a “hydrophilizing agent”.
  • Suitable hydrolyzable organometallic compounds (a) for the present invention include, for example, those of formula (I):
  • a is 0 or an integer from 1 to 6, b is 0 or an integer from 1 to 5, c is 0 or; An integer from 6 to 6 (where a + b + c ⁇ 3 and a and c are not simultaneously 0), and X is the same or different O-, N-, F- and Z- or chlorine-containing monovalent organic groups having 1 to 5,000 carbon atoms or hydrogen atoms, and M is small
  • a metal atom having a valence of trivalent R 1 is the same or different and each represents an oxygen atom, a nitrogen atom, a fluorine atom and / or a chlorine atom.
  • Hydrolyzable organometallic compound Re that, its O Li sesame over or of two or more or al Ru Nobi Li sesame one there down et been ing the organometallic compound.
  • the compounds that can be used are described in detail in WO 97 11130 Novel fret.
  • a is an integer of 0 or 1 to 6 from the viewpoint of surface concentrating property, hydrolyzing property, and desorbing property; It is preferably an integer from 2 to 4.
  • b is an integer of 0 or 1 to 5 from the viewpoint of surface enrichment and hydrophilicity And preferably an integer of 0 to 1, and
  • c is an integer of 0 or 1 to 6 from the viewpoint of surface concentrating, hydrolyzing and desorbing properties. It is preferably an integer from 0 to 3.
  • the total amount of a, b and c is determined by the valency of the metal atom M, but in the formula (I), either OR 1 or R 2 is used. One of them is necessary for its anti-bioadhesive properties, anti-fouling adhesive properties, surface condensing properties, and hydrolyzability (hydrophilizing ability), so that a and c do not become 0 at the same time.
  • the total amount of a, b and c is at least 3.
  • X is a hydrogen atom, or an oxygen atom, a nitrogen atom, a fluorine atom, or a chlorine atom, as in (i) to (iii) above.
  • Examples of these are, for example, CH 3 , CH 3 CH 2 , CH 3 CH 2 CH 2 , (CH 3 ) 2 CH, CF 3 CH 2 , CF 3 CF 2 CH 2 , (CF 3 ) 2 CH, F (CF 2 ) 4 CH 2 CH 2 , F (CF 2 ) 8 CH 2 CH 2 , H (CF 2 ) 4 CH 2 etc., but surface concentrating and hydrolyzing In terms of detachability CF 3 CF 2 CH 2 (CF 3 ) 2 CH is preferred.
  • OCN CH 2 ) 3 CH 30 (CH 2 CH 20 ) 5 (CH 2 ) 3 is preferred in terms of hydrophilicity, compatibility, and adhesion.
  • the organic group X is a polymerizable organic group which may contain, for example, an oxygen atom, a nitrogen atom, a fluorine atom, a chlorine atom, a silicon atom, and the like. The group is removed.
  • the molecular weight obtained by polymerizing or copolymerizing the compound represented by the formula (I) having such a polymerizable organic group is 200,200,000. Also, preferably 5000 to 20000 polymers or copolymers are included in the present invention.
  • R 1 may contain the same or different oxygen, nitrogen, fluorine, and / or chlorine atoms, and may be bioadherent. Monovalent with 11000 carbons in terms of prevention, surface concentration, hydrolyzability (hydrophilicity), and desorption It is an organic group or a hydrogen atom, and the number of carbon atoms is preferably from 1 to 100, and more preferably from 1 to 16. No. However, at least one of R 1 is CF 3 CH FCF 2 CH 2 , CF 3 CHFCF 2 CHCH 3 or CF 3 CHFCF 2 C (CH
  • R 1 other than CF 3 CHFCF 2 CH 2 , CF 3 CHFCF 2 CHCH 3 and CF 3 CHFCF 2 C (CH 3 ) 2 are as follows.
  • organic groups are, for example, CF 3 CH 2 , CF 3 CF 2 CH 2 , CF 3 (CF 2 ) 2 CH 2 , CF 3 (CF 2 ) 3 CH 2 CH 2 , (CF
  • R 2 may be the same or different, and has excellent chelating ability even if it contains a fluorine atom or a chlorine atom. It has a carbon number of 1 to 20 in terms of bioadhesion prevention, surface thickening, hydrolyzability (hydrophilicity), and desorption properties. A value of ⁇ 10 is a preferred organic group.
  • a water-decomposable organic metal compound to which an organic base having such a capability of binding is combined is used.
  • excellent storage stability, anti-bioadhesive properties, reactivity, solubility, and compatibility can be obtained.
  • Compounds that can be such organic compounds that have the ability to chelate include, for example, 2,41 pentanes, 2,4 pentanes, 4 _ Heptanedione, etc.] 3-Ketostears such as diketons, methyl acetate acetate, ethyl acetate acetate, butylacet acetate, etc.
  • Lactic acid methyl lactate, methyl lactate, ammonium lactate, salicylic acid, methyl salicylate, methyl ethyl salicylate, linoleic acid Hydroxycarboxylic acids such as formic acid, ethyl linoleate, tartaric acid, and ethyl tartrate, or their esters, salts, and 4-hydroxy acids 4—Methyl 1—2—pentanone, 4—Hydroxy — 2—Pen 2—Non, 4-Hydroxy 1—2—Heptanone, 4—Hydro Roxie I 4 _Me Chil_2—Cetolic alcohols such as heptanones, monoethanolamines, diethanolamines, and triethanolamines Amin, N-methylmonoamine, N-methylamine, N_methylmonoethanol, Amin, ,, ⁇ -methylethanol Amino alcohols such as min, ⁇ , ⁇ -ethyl ethanol
  • the metal atom M is, for example, B, Al, Ga, In, Tl, Sc, Y, La, Ac, Si, Ge, Sn, Pb, Ti, Zr, Hf, As, Sb, Bi, V , Nb, Ta, Te, Po, Cr, Mo, W, At, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Pd> Os, Ir, Pt, etc.
  • Al, Ti, B, Zr or Si, particularly Si is preferred.
  • organometallic compound represented by the formula (I) for example, an organometallic compound as described above, or a polyolgomer or a coli obtained therefrom can be used. Sesame sesame etc. are excreted.
  • the oligomers or oligomers such as linear, branched, cyclic, and three-dimensional are exemplified. can give .
  • the degree of polymerization of the oligomer or the oligomer is preferably from 2 to: 1000, and more preferably from 4 to: 100. As the degree of polymerization decreases, the boiling point of the oligomers or oligomers tends to be low, and the oligomers or oligomers tend to volatilize during coating and are incorporated into the coating film It becomes difficult.
  • the polymerization degree of the oligomer and the oligomer can be controlled by the molar ratio of the water to be reacted and, for example, the organometallic compound represented by the formula (I). For example, when [H 2 O] / [organometallic compound represented by the formula (I)] is reacted at a mole ratio in the range of 0.4 to 0.95, polymerization occurs. Oligomers or kooligomers having a degree of about 2 to 20 can be obtained.
  • the composition ratio (mol) of a unit constituting a coco ligomer obtained by using two kinds of organometallic compounds represented by the formula (I) as the coco ligoma The ratio is preferably 1 Z 9 to 9/1.
  • the GPC molecular weight (value converted into polystyrene using tetrahydrofuran as an eluent) of an oligomer or a cooler is 500-500 by weight average molecular weight. A value of 10,000 is preferred, and a value of 1,000 to 5,000 is even more preferred. As the molecular weight decreases, the effect of hydrophilization decreases, and when the molecular weight exceeds 10,000, gelation tends to occur during synthesis and during storage.
  • the organometallic compound represented by the above formula (I) can highly hydrophilize the surface of a coating film by the action of its hydrolyzable group, and has anti-bioadhesive and anti-fouling properties. It is possible to provide a coating composition having excellent adhesion, low chargeability and anti-fog property.
  • At least one of R 1 and R 2 is CF 3 CHFCF 2 CH 2 , CF 3 CHF CF 2 CHCH 3 or CF 3 CHFCF 2 C (CH 3 ) 2 , for example, has excellent surface enrichment, reproducibility of surface hydrophilicity, and blocking resistance. The effect is obtained.
  • the content of fluorine atoms in the organometallic compound represented by the formula (I) is at least 5% by weight, preferably 15 to 60% by weight.
  • a resin for a binder is basically a film-forming agent or a film-forming agent for retaining a hydrolyzable organic metal compound (a).
  • a resin for a binder is basically a film-forming agent or a film-forming agent for retaining a hydrolyzable organic metal compound (a).
  • a hydrolyzable organic metal compound
  • solvent-soluble resin As such a resin (b), a solvent-soluble resin is preferable because it is easy to form and form a coating film.
  • Solvent-soluble resins include, for example, fluororesin, thermoplastic acrylic resin, acrylpolyol resin, acrylsilicon resin, and fluorosilicone resin. Examples include non-fluorinated solvent-soluble resins such as silicone resin and inorganic materials. Among the non-fluorine-based solvent-soluble resins, thermoplastic acrylic resin, acrylic polyol resin, and inorganic materials have been used from the viewpoint of their use results. I like it.
  • the solvent-soluble fluororesin used in the present invention has been known in the art, it is known that the ethylene-tetrafluoroethylene copolymer (ETFE) Highly hydrophobic, similar to heat-meltable fluororesins insoluble in solvents such as tetrafluoroethylene copolymers and other solvents such as hexafluoropropylene copolymer (FEP) However, there is a similar problem in terms of the ability to prevent adhesion to living bodies and contamination.
  • ETFE ethylene-tetrafluoroethylene copolymer
  • FEP hexafluoropropylene copolymer
  • a hydrolyzable group can be used. This is preferable because the organometallic compound containing sulphate is collected on the surface during film formation, and the action of hydrophilizing the surface is strengthened.
  • Solvent-soluble fluororesins that can be particularly preferably used in the present invention include, among conventionally known organic solvent-soluble fluororesins,
  • the crystal melting point is 100-180t, preferably 100-: 150t:
  • Particularly preferred are those that have more than one of these properties.
  • fluororesins are required, but not limited thereto.
  • fluorine-based, hydrocarbon-based, and other monomers having radical polymerizability can be used, and in particular, TFE , Perfluorovinyl ether, vinylidene fluoride, bifluoride, black mouth trifluoroethylene, etc. .
  • This solvent-soluble fluororesin has a fluorine content of 60% by weight or more, a refractive index of 1.39 to 1.27, is amorphous, and has a glass transition. point Is 70-250t: Commercially available products include Teflon AF series (manufactured by Dupont).
  • fluorine-based, hydrocarbon-based, and other monomers having radical polymerizability can be used.
  • TFE perfluorovinyl ether
  • VdF vinyl fluoride
  • tri-fluoroethylene in the mouth can be used.
  • This solvent-soluble fluororesin has a fluorine content of 60% by weight or more, a refractive index of 1.39 to: I.27, and is amorphous and glassy. The transition point is 70-250.
  • Examples of commercially available products include a site manufactured by Asahi Glass Co., Ltd.
  • fluoropolymers As other monomers, fluoropolymers, hydrocarbons, and other monomers that have a radical polymerizability can be used. Specifically, for example, TFE , Perfluorovinyl ether, vinylidene fluoride, vinyl fluoride, tri-fluoroethylene, etc.
  • This solvent-soluble fluorine resin has a fluorine content of 60% by weight or more, a refractive index of 1.39 to: 1.27, and is amorphous and glass. The transition point is 70-250.
  • As a commercially available product there is a site manufactured by Asahi Glass Co., Ltd.
  • the composition ratio of the monomer is TFE 10 to 50 %, HFP 0 ⁇ 50mol% and VdF 90 ⁇ : 10mol%, preferably TFE / HFPZ VdF 10 ⁇ 30Z 3 ⁇ 40/77 ⁇ 40 force It is a thing.
  • This copolymer may be modified with an isocyanate compound or the like.
  • This solvent-soluble fluororesin has a fluorine content of 60% by weight or more, a refractive index of 1.39 to: 1.27, and a crystal melting point of 100 to: I80. belongs to . Examples of commercially available products include THV series (manufactured by Sumitomo SLIM Co., Ltd.).
  • a solvent-soluble fluororesin for example, a fluorosol having a hydroxyl group or a carboxyl group which is soluble in a solvent is used.
  • Thinner copolymers are required. Specific examples include, for example, Japanese Patent Publication No. 60-21686, Japanese Patent Publication No. 3-121107, Japanese Patent Publication No. 4-279612, Japanese Patent Publication No. 4-28707, Japanese Patent Publication No. 2-232221. Such publications as described in each gazette are given.
  • the number average molecular weight (according to GPC) of the copolymer is from 1,000 to 100,000, preferably from 1500 to 30,000. If the molecular weight is less than 1,000, the curability and weather resistance tend to be insufficient, and if it exceeds 100000, there is a tendency for problems in workability and coatability.
  • the hydroxyl value of the copolymer is from 0 to 200 (mgKOH / g), and preferably from 0 to: ISO mgKOHZg.
  • amount of the hydroxyl group is reduced, curing tends to be poor, and when it exceeds 200 (mgKOHZg), a problem tends to occur in the flexibility of the coating film.
  • the acid value of the copolymer is from 0 to 200 (mgKOH / g), and from 0 to; OO (mgKOHZg) is even more preferred. If the acid value is low, curing tends to be poor, and if the acid value exceeds SOOimgKOHZg), the coating film will be flexible. There is a tendency for problems with gender.
  • a fluororefin-based copolymer is used from the viewpoints of bioadhesion-preventing property, anti-contamination-adhesion property, decontamination-removing property, and anti-pollution property. You can do whatever you want.
  • copolymer examples include Zefful manufactured by Daikin Industries, Ltd., Lumifuron manufactured by Asahi Glass Co., Ltd., and Cefra manufactured by Central Glass Co., Ltd. Commercial products such as LeCoat, Fluoronet manufactured by Dainippon Ink and Chemicals Inc., and Zaflon manufactured by Toa Gosei Co., Ltd. are available.
  • non-fluorine-based solvent-soluble resin for example, a special resin is used.
  • thermoplastic acrylic resins include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methyl acrylate.
  • Methacrylic acid esters such as acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and butyl acrylate Homopolymers of acrylates such as latex, copolymers of these, or copolymers of these with a copolymerizable monomer. It is.
  • the copolymerizable monomer include aromatic biel compounds such as styrene, acrylonitrile, various vinyl ethers, aryl ethers, and the like.
  • Various vinyl compounds such as vinyl esters, unsaturated monomers having a functional group such as a carboxyl group, an amino group, an epoxy group, and the like are required. .
  • thermosetting acrylic resin examples include acrylpolyol resin and acrylsilicon resin.
  • acrylic polyol resin examples include (a) a hydroxyl group-containing (meth) acrylic acid ester and hydroxyvinyl. Hydroxyl-containing ethylenically unsaturated monomers such as ether and aryl alcohol, and (b) hydroxyl-free olefins; Vinyl ether, aryl ether, vinyl ester, pulp vinyl ester, (meta) acrylic acid ester, vinyl Aromatic compounds, (meta) acrylonitrile, unsaturated monomers containing carboxyl groups, unsaturated monomers containing epoxy groups, and amino groups A polymer with a hydroxyl-free unsaturated monomer such as an unsaturated monomer is used.
  • the acrylic polyol resin may have a hydroxyl group, a carboxyl group, an epoxy group, or an amino group.
  • the hydroxyl value of the acrylic polyol resin is from 0 to 200 (mgKOH / g), and preferably from 0 to 100 (mgKOHZg). If the hydroxyl value is too low, curing tends to be poor, and if it exceeds SOOimgKOHZg), there is a problem in the flexibility of the coating film. There is a direction.
  • the acid value of the acrylic polyol resin is 0 to 200 (mgKOH / g), and more preferably 0 to 100 (mgKOH / g). It is better. If the acid value is too low, curing tends to be poor, and if it exceeds 200 (mgKOH / g), there is a problem in the flexibility of the coating film. Tend .
  • Acrylic polyol resins include, for example, Dianal made by Mitsubishi Rayon Co., Ltd., and Dainippon Ink Chemicals Co., Ltd. This product uses marketed products such as Acrylic, Hitachi, Ltd., Hitaroid Co., Ltd. and Mitsui Toatsu Kagaku Co., Ltd. And are confused.
  • the aforementioned acrylic silicone resin has, for example, at least one silane group and one radically polymerizable unsaturated group in one molecule.
  • Replace the existing acrylic monomer with the hydroxyl It may be one which has been polymerized with the group-containing ethylenically unsaturated monomer (a) and Z or its hydroxyl-free unsaturated monomer (b). .
  • the acrylic silicone resin may have a hydrolyzable silyl group, a hydroxyl group, or an epoxy group.
  • Acrylic silicone resins include commercially available products such as Zemrack manufactured by Kanegafuchi Kagaku Kogyo Co., Ltd. and Krymar Co., Ltd. manufactured by Sanyo Kasei Kogyo Co., Ltd. Can be used.
  • the non-hydrogen-containing non-hydrolyzable group-containing metal such as Si, Ti, A1, etc.
  • Inorganic materials such as non-hydrolysable group-containing organopolysiloxanes, non-fluorine-containing metals (such as Si, Ti, and A1) and alcohols can also be used. .
  • the inorganic materials include, for example, Toray Industries, SH, SR and DC series manufactured by Silicone Corporation, and Shin-Etsu Chemical Co., Ltd.
  • silicone resins such as KR series (KR_255, KR-300, KR-500, KR-212) and X-22-8904, manufactured by Gunze Sangyo Co., Ltd. Launched Ecotone, Nihon Synthetic Rubber Co., Ltd. glass power, Tobe Co., Ltd. porcelain, Nihon Yushi Yushi Co., Ltd.
  • fluorine-containing silicone resin examples include, for example, those described in JP-A-4-1279612. .
  • Epoxy resins include, for example, Epikote Series manufactured by Yuka Shell Co., Ltd.
  • Polyester resins and alkyd resins include, for example, Bekkozol series and super-products manufactured by Ink Chemicals Co., Ltd. of Japan. -Becco Rose Series, Stille Resole, Becco Light Series, Sino, etc. Ichigo Kakko Kogyo Co., Ltd.'s full-kid series and Esper series, such as the Becco Light Series and the Burnock Series. The throat is destroyed.
  • amino resin for example, Pekka Min Series and Super Beck Min Series manufactured by Dainippon Ink and Chemicals, Inc. And other products, such as Melanseries, manufactured by Hitachi Chemical Co., Ltd .; Cymer Series, manufactured by Mitsui CyAnamid Inc .; and Mitsui Toatsu Chemicals, Inc.
  • the resin composition of the present invention contains a hydrolysis accelerator (c) in order to promote hydrolysis and promote hydrophilicity, and to quickly and effectively exert a bioadhesion preventing ability. You may.
  • Metal chelates such as aluminum chelates, titanium chelates, and zirconium chelates are examples of hydrolysis promoters.
  • organic tin compounds, organic acid phosphate esters, organic titanate compounds, reaction products of acid phosphate esters with amines, saturated or unsaturated compounds examples include polyvalent carboxylic acids, their anhydrides, and organic sulfonic acids.
  • the amount of the hydrolysis accelerator (c) to be added is about 0.01 to 20 parts with respect to 100 parts of the resin (b), and 0.01 to 10 when the pot life is long. Department The degree is preferred.
  • a known compound having the formula (I) may be used in an amount of 50 parts or less, preferably 0.05 to 50 parts, per 100 parts of the solid component of the resin (b).
  • Examples of commercially available diatom adhesion preventive agents include, for example, Net King 300 manufactured by Keiai Densei Co., Ltd., Net King 400, and Tobe Co., Ltd. Clean fish 5000 etc. are required.
  • a known repellent that prevents the access of aquatic organisms without releasing harmful substances such as heavy metals and the like is used.
  • 0.05 to 50 parts may be added.
  • biorepellents have the formula:
  • R 5 is the same or different, and each is an alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, or all or a part of halo.
  • X is H or a halogen atom, preferably C1 F or F
  • a nitrogen-containing amide-type repellent represented by the formula:
  • R 5 X (Wherein, R 5 and X are the same as described above), and flavonoid-type repellents represented by the formula (1) are exemplified.
  • Examples include BioDan G, BioDan GPA, BioClin P, and KS-339 manufactured by Idanari Co., Ltd.
  • a curing agent is added.
  • a curing agent may be appropriately selected from known curing agents depending on the crosslinking reactive group of the curable resin.
  • isocyanates are preferred as low-temperature curing agents, and commercial products are preferred. Examples include the Colony Series manufactured by Japan Polyurethane Industry Co., Ltd., and the LTI manufactured by Kyowa Hakko Co., Ltd.
  • the compounding amount is preferably about 0.1 to 30 parts with respect to 100 parts of the curable resin (b).
  • the resin (b) a resin that is soluble in an organic solvent is preferred.
  • an organic solvent is added to the composition.
  • the organic solvent may be fluorine-based or non-fluorine-based, but as the resin (b), a fluorine-containing resin, particularly a fluorine-containing resin having a fluorine content of 60% or more is used.
  • fluorine-based organic solvents are preferred in terms of the solubility of the fluororesin, the transparency of the obtained film, and the like.
  • fluorine-based organic solvents examples include CF 3 CH 2 OH, F (CF 2 ) 2 CH 2 (H, (CF 3 ) 2 CHOH, F (CF 2 ) 3 CH 2 OH, F Fluorine alloys such as (CF 2 ) 4 C 2 H 5 OH, H (CF 2 ) 2 CH 2 ⁇ H, H (CF 2 ) 3 CH 2 OH, H (CF 2 ) 4 CH 2 ⁇ H Cooling solvent; Emissions zero emissions, meta key sheet les down to key support full o la I de, etc.
  • Non-fluorine-based organic solvents include, for example, hydrocarbons such as xylene, toluene, solbeso 100, solirebeso 150, and hexane.
  • Solvents methyl acetate, ethyl acetate, ethyl acetate, ethyl glycol acetate monomethyl ether, ethyl acetate glycol monoethyl acetate Chill ether, ethyl acetate alcohol monobutyrate ether, diethyl acetate alcohol monomethyl ether, ethyl acetate Long glycol monoethyl ether, diethyl alcohol monobutyrate ether, ethyl alcohol methyl alcohol, acetic acid Ester-based solvents such as ethylene glycol; dimethyl ether, dimethyl ether Relay, dibutyl ether, ethyl glycol monomethyl ether, ethyl glycol monoethyl ether, eth
  • a mixture of a fluorine-based solvent and a non-fluorine-based solvent may be used.
  • the organic metal compound is 0.1 to 50 parts per 100 parts of the resin (b), and 1 to 50 parts. Preferably it is 30 copies. If the amount is less than 0.1 part, the water-repellent effect on the surface (anti-bioadhesive property) will be reduced. descend .
  • the mixing ratio is 1 to 2000 parts with respect to 100 parts of the solvent-soluble resin (b). It is more preferable that the amount be 100 to 150 parts in view of shape, film forming property, curability, and appearance of the coating film.
  • an alcohol-based solvent is used as an organic solvent, and the above-mentioned curing agent has a high reactivity with alcohol, such as a room-temperature-curable isosilicate. In such a case, it is preferable that the alcohol-based solvent is 1 to 15 parts, and the type of the alcohol-based solvent is 2 or 3 grade. Le Colle is preferred.
  • the resin composition of the present invention may be used to form a coating film on the surface of a product or structure by painting, or it may be a casting method or an extrusion method. It may be molded as a single molded product such as a film, sheet, or tube.
  • Additives include, for example, surface conditioners, pigments, pigment dispersants, thickeners, leveling agents, defoamers, film-forming aids, ultraviolet absorbers, HALS, and anti-glare.
  • Inhibitors fillers, colloidal silicas, antifungal agents, silane coupling agents, anti-skinning agents, antioxidants, flame retardants, anti-sagging agents, antistatic Agents, protective agents, and water-soluble resins (polyvinyl alcohol, polyethylene oxide, etc.).
  • the surface conditioner not only prevents unevenness after painting and improves leveling properties, but also contributes to preventing the color from being separated in the color paint and preventing color floating.
  • the addition is optional, and if necessary, a known one may be used.
  • an appropriate antifoaming agent when added, the defoaming property is improved without significantly impairing the surface hydrophilicity.
  • Suitable antifoaming agents include, for example, long-chain fluoroalkyl-modified siloxanes of Zeffle GH-200 (manufactured by Daikin Industries, Ltd.).
  • Fluorosilicone-based defoamers such as siloxane-based defoamers such as FA-600 and FS-126265 (both manufactured by Shin-Etsu Chemical Co., Ltd.) And silicone compound-based antifoaming agents, silicone-based antifoaming agents, and acrylic-based antifoaming agents.
  • the resin composition of the present invention may be used for forming a coating film as a coating composition, or may be used as a molding material for a film, a sheet, or a tube. It may be molded into any shape.
  • Various painting methods can be used, such as spraying, brushing, rollers, curtains, rolls, and dips.
  • the coating composition various forms such as clear, solid, and compounding of filler (filament) can be adopted.
  • the molding method include a casting method, an extrusion method, an injection method, and a blow method.
  • a molded article such as a coating film or a film having a surface having a hydrophilicity can be obtained.
  • the thickness of the coating film may be determined as appropriate according to the application and use environment. It can be selected from the range of ⁇ 2 mm.
  • the surface of the base material (resin (b)) may be subjected to blast treatment, corona discharge treatment, ozone treatment, etc.
  • a middle coating layer may be provided.
  • durability can be improved by performing such treatments as desired.
  • the surface of the coating film or molded article formed by the composition of the present invention is easily and highly hydrophilized, and does not allow aquatic organisms and physiological substances to adhere and grow. As a result, it is possible to obtain anti-fouling properties, not to adhere lipophilic dirt, and to achieve anti-fouling properties.
  • fluorocarbon resin when fluorocarbon resin is used, it has a high degree of weather resistance, chemical resistance, optical properties (such as transparency), mechanical properties (strength and elongation), It has excellent adhesiveness, heat resistance, and heat yellowing resistance.
  • the resin composition of the present invention provides a highly hydrophilic coating layer or film having a surface contact angle with water of less than 70 degrees and even 55 degrees or less. You can do it.
  • the resin composition of the present invention can be applied to various water surfaces or objects or structures used in water regardless of seawater or freshwater.
  • the adhesion rate of the Fujibo is less than 15%, preferably less than 5%, especially less than 5% in the following zippo adhesion test.
  • the resin composition of the present invention not only can prevent the aquatic organisms from adhering, but also can easily remove the aquatic organisms even if they adhere and grow to some extent.
  • Test sample Structural sample subjected to the above-mentioned Fujipo adhesion test for 60 days
  • Rinse conditions Dispense tap water at right angles to the sample surface for 20 seconds so that the water pressure is 0.3 ⁇ 0.05MPa on the sample surface.
  • the present invention also relates to a medical member, film, or sheet having a coating layer obtained from the resin composition of the present invention on the surface as described above.
  • the present invention relates to a medical member comprising a molded article having a shape such as a tube or a tube.
  • the resin composition is used on the surface of water or in water, or is obtained from the resin composition on one surface of a medical marking film, that is, one surface of a resin film.
  • the present invention also relates to a film having a coating layer and a pressure-sensitive adhesive layer on the other surface.
  • the resin film used as the base material for such a marking film is not particularly limited as long as it has excellent water resistance, strength, and flexibility. No. A specific example is salt, for example. Vinyl resin, polyester resin, silicone resin, elastomer class, fluorine resin, urethane resin, polyamide resin, poly resin Refines (Polyethylene, Polypropylene, etc.) are required.
  • pressure-sensitive adhesive forming the pressure-sensitive adhesive layer conventionally known pressure-sensitive adhesives can be used. Typical examples thereof include epoxy resin-based, amino resin-based, and acrylic resin-based pressure-sensitive adhesives. Adhesives such as lilyl resin, vinyl resin (such as vinyl acetate polymer), curable acrylic resin, and silicone resin are exfoliated. .
  • composition of the present invention can be applied to various types of base materials, it prevents bio-adhesion to a wide range of materials and structures and prevents bio-substance adhesion. Can be imparted with durability.
  • the substrate include a metal-based substrate, a cement-based substrate, a plastic-based substrate, and the like.
  • metal base material examples include iron and its chemical conversion products or plating materials, aluminum and its chemical conversion products, stainless steel and the like. And the chemicals to be treated.
  • cement-based material examples include cements, limes, cements, concrete, cement cement, and asbestos. Rate, gypsum board, etc. are excavated.
  • plastic base examples include polychlorinated vinyls, polyesters, polycarbonates, and acrylics. , Polyolefins, Polystyrenes, Polyurethanes, Polyamides, Nylons, Natural rubbers, Urethanes Such as rubber and ABS resin.
  • the undercoat paint or the middle paint is applied, for example, and then the paint composition of the present invention is applied. This is because of the anti-corrosion properties and adhesion between phases. I like it.
  • zinc paint is preferred as the primer.
  • the undercoating paint and the intermediate coating paint are preferably epoxy resins (including those having an evening change and a urethane change), vinyls. At least one resin selected from the group consisting of resin (including tar modification and acrylic resin), rubber chloride, polyurethane resin, and phenol resin.
  • each of the base coat and the middle coat is 1! A thickness of up to 2 mm, preferably 5 to 500 ⁇ m, is suitable.
  • the base material is a plastic base material
  • the base material used for the metal base material, the cement base material, and the undercoat paint and the intermediate coat paint are applied. Thereafter, the coating composition of the present invention can be applied.
  • the coating method is, for example, Gravia Co., Ltd. There are various methods such as the ringing method, doctor blade method, roll coat method, linole roll method, and Jay-Nay coat method.
  • the coating film thickness should be from 1 to 25111, preferably from 1 to 15 ⁇ m, in terms of coating appearance and paintability. It is.
  • TFE-based hardening resin Varnish (Daikin Industries Zeffle GK-500 manufactured by Co., Ltd. Resin concentration 60%, resin hydroxyl value eOmgKOHZga or less, called “TFE copolymer”), and a polyisocyanate curing agent (LTI manufactured by Kyowa Hakko Co., Ltd.) ) In such an amount that the NCOZ OH equivalent ratio becomes 1.0, and further as a hydrolyzable group-containing organometallic compound of the formula (V):
  • AM-712 treated chemical aluminum plate is coated three times with Nippon Paint Co., Ltd. epoxy resin paint (Hibon 20 Ace) to dry film thickness of about 100 / zm.
  • the undercoat layer of DuPont SF which is a urethane intermediate paint manufactured by Nippon Paint Co., Ltd., is applied twice and dried.
  • Medium coated dry film thickness of about 70 ⁇ .
  • the paint varnish obtained above was spray-painted (overpainted) on the middle coat, cured for 1 hour at room temperature, and dried at 80 for 20 minutes. As a result, a test coated plate (dry film thickness: about 30 / m) was prepared.
  • the coated plate After 60 days from the start of the test, the coated plate is pulled up, and the number of fuspo adhered to the coated plate is measured with a stereoscopic microscope, and the number (n) and the adhesion ratio ((n / 600) ) X 100%].
  • the coated plate (including all that had no fuspo attached) that had been subjected to the above-mentioned fusippo adhesion test for 60 days was coated with 0.3 ⁇ 0 water on the surface of the lacquered plate. Water was released at a right angle for 20 seconds so that the water pressure became 05 MPa, and washed, and then adhered in the same manner as in the bioadhesion test (remaining).
  • the number of zippo bodies (m), the residual ratio of Fujibo [(mZ600) X 100%], and the residual degree of diatoms (visual appearance and color difference) can be examined.
  • the number of killed individuals of Fujipo that released the effects of the harmful components eluted from the painted board (k.
  • the amount of harmful metals (Cu, Sn, and Zn) harmful to the environment was determined by the high frequency induction plasma method (306 Super, manufactured by Hitachi, Ltd.). Scan. Adjust the concentration of the sample so that the detection limit is 0.1 ppm).
  • a coating resin resin varnish was prepared in the same manner as in Example 1 except that the components shown in Table 1 were used in the amounts shown in the table. Next, each varnish was coated on a chemically treated aluminum plate (those treated with the same undercoating as in Example 1) as in Example 1 and subjected to the test. A painted plate was prepared. In the same manner as in Example 1, the test coating plate was examined for the degree of hydrophilicity of the coating film, the ability to prevent bioadhesion, the ability to remove the living body, and the degree of environmental impact. Table 2 shows the results.
  • p is Ri Ah at 4
  • R is Ri Oh in CH 3 your good beauty CH 2 C 2 F 5
  • Ru Oh in CH 2 C 2 F 5 CH 3 ratio is 0.3 compounds.
  • R is CH 3 and CH 2 CF 2 CFHCF 3 , and the ratio of CH 2 CF 2 CFHCF 3 Z CH 3 is 0.3.
  • D p is Ri Ah with 4, R is Ri Ah in CH 3 Contact good beauty CH 2 CF 2 CFHCF 3, CH 2 CF 2 CFHCF 3 Z CH 3 ratio Ah Ru compound 0.5.
  • Alumichelate D Alumichelate compound manufactured by Kawaken Fine Chemicals Co., Ltd.
  • Example Resin Hardener Organometallic compound
  • a Hydrolysis Surface conditioner No. Quantity (PHR) Accelerator (PHR) Amount (PHR)
  • thermoplastic VdF copolymer varnish (LC 930 manufactured by Daikin Industries, Ltd., resin concentration: 45%; hereinafter, referred to as “VdF copolymer A”)
  • a coating varnish was prepared in the same manner as in Example 1 except that the components shown in Table 3 were used in the amounts shown in the same table (NK2 cup viscosity: 15 seconds).
  • each varnish was applied to a chemical conversion-treated aluminum plate (the same undercoating treatment as in Example 1) as in Example 1 to prepare a test coated plate.
  • the test coated plate was examined for the degree of hydrophilicity of the coating film, the ability to prevent bioadhesion, the ability to remove living organisms, and the degree of environmental impact. Table 4 shows the results. Table 3
  • Example Resin Curing agent Organometallic compound (a) Hydrolysis Surface conditioner No. Quantity (PHR) Accelerator (PHR) Type Quantity (PHR)
  • VdF-based copolymer B a thermoplastic VdF-based copolymer (THV-200P, manufactured by Sleem Co., Ltd .; hereinafter, referred to as “VdF-based copolymer B”) is used as methylethyl ketone Z butyl acetate.
  • VdF-based copolymer B a thermoplastic VdF-based copolymer
  • a varnish with a resin concentration of 25% was prepared by dissolving in a mixed solvent.
  • a coating varnish was prepared in the same manner as in Example 1 except that this varnish and the components shown in Table 5 were used in the amounts shown in the same table (the viscosity was methylethyl ketone butyl acetate (butyl acetate).
  • Example Resin Curing agent Organometallic compound (a) Hydrolysis Surface conditioner No. Quantity (PHR) Accelerator (PHR) Type Quantity (PHR)
  • Fujibobo adhesion Diatom adhesion Fujibobo removal ⁇ :: Bare ⁇ ⁇ Fujibobo mortality
  • thermosetting acrylic resin varnish (Acrylic A-801 manufactured by Dainippon Ink and Chemicals, Inc .; resin concentration 50%, resin hydroxyl group) 100 mg KOHZg, hereinafter referred to as “thermosetting acrylic resin”), and a polyisocyanate-based curing agent (Nippon Polyurethane Industrial Co., Ltd.)
  • thermosetting acrylic resin a thermosetting acrylic resin varnish
  • polyisocyanate-based curing agent Nippon Polyurethane Industrial Co., Ltd.
  • each varnish was coated on a chemically treated aluminum plate (those that had been subjected to the same undercoating as in Example 1) as in Example 1, and the test coated plate was applied. It was made.
  • the degree of hydrophilicity of the coating film, the ability to prevent bioadhesion, the ability to remove living organisms, and the degree of environmental impact were examined in the same manner as in Example 1. Table 8 shows the results.
  • Example Resin (b) Hardener Organometallic compound (a) Hydrolysis Surface conditioner No. Quantity (PHR) Accelerator (PHR) Planting amount (PHR)
  • thermoplastic acrylic resin (BR-773 manufactured by Mitsubishi Rayon Co., Ltd .; hereinafter, referred to as “thermoplastic acrylic resin”) was converted to butyl acetate. After dissolution, a varnish with a resin concentration of 35% was prepared. A paint varnish was prepared in the same manner as in Example 1 except that this varnish and the components shown in Table 9 were used in the amounts shown in the same table (NK2 cup viscosity 15 Seconds). Then, each of the paints was applied to a chemically treated aluminum plate (the same as in Example 1 that had been subjected to the undercoating and undercoating treatment) in the same manner as in Example 1; Was made. Using this test coated plate, the degree of hydrophilicity of the coating film, anti-bioadhesive properties, bioremovability, and environmental impact were examined in the same manner as in Example 1. The results are shown in Table 10. Table 9
  • Example Resin Hardener Organometallic compound
  • a Hydrolysis Surface conditioner No. Quantity (PHR) Accelerator (PHR) Amount (PHR)
  • Epoxy resin varnish (Epicoat EP1001X70 manufactured by Yuka Shellepoxy Co., Ltd.) as resin (b), hereinafter referred to as "epoxy resin” )
  • an amine-based curing agent (EpoMate S 2002, manufactured by Yuka Shiel Epoxy Co., Ltd.) in an amount such that the equivalent ratio becomes 1.0.
  • a paint varnish was prepared in the same manner as in Example 1 except that this varnish and the components shown in Table 11 were used in the amounts shown in the table. Adjust the NK2 pump viscosity to 15 seconds with a ren and then apply each varnish in the same manner as in Example 1 to a chemically treated aluminum plate (undercoating in the same manner as in Example 1). The intermediate coating was applied) to prepare a test coated plate.
  • Example Resin (b) Hardener Organometallic compound (a) Hydrolysis Surface conditioner No. Type Amount (PHR) Accelerator (PHR) Amount (PHR)
  • a room temperature film-forming silicone resin varnish (KR-251 manufactured by Shin-Etsu Chemical Co., Ltd .; hereinafter, “Silicone Resin A ), And the varnish for paint was prepared in the same manner as in Example 1 except that this varnish and the components shown in Table 13 were used in the amounts shown in the same table. It was manufactured (adjusted to NK 2 force viscosity of 15 seconds with Xylene). Next, each varnish was coated on a chemically treated aluminum plate (the same as in Example 1 that had been subjected to the undercoating and intermediate coating) in the same manner as in Example 1. Then, a test coated plate was prepared. Using this test coated plate, the degree of hydrophilicity of the coating film, the ability to prevent bioadhesion, the ability to remove the living body, and the environmental impact were examined in the same manner as in Example 1. The results are shown in Table 14.
  • Example Resin Hardener Organometallic compound
  • a Hydrolysis Surface conditioner No. Quantity (PHR) Accelerator (PHR) Amount (PHR)
  • a room temperature film-forming silicone resin resin (X-040-175, manufactured by Shin-Etsu Iridaku Kogyo Co., Ltd.). And the components shown in Table 15 were used in the amounts shown in the table, except that this varnish was used in the same manner as in Example 1 to prepare a paint varnish. Prepared (adjusted to NK 2 force viscosity of 15 seconds with Xylene). Next, each varnish was coated on a chemically treated aluminum plate (which had been subjected to the same undercoating process as in Example 1) in the same manner as in Example 1 and subjected to the test. A painted plate was prepared. Using this test coated plate, the degree of hydrophilicity of the coating film, the ability to prevent bioadhesion, the ability to remove biomaterials, and the degree of environmental impact were examined in the same manner as in Example 1. The results are shown in Table 16.
  • Example Resin (b) Hardener Organometallic compound (a) Hydrolysis Surface conditioner No. Type Amount (PHR) Accelerator (PHR) Amount (PHR)
  • a cuprous oxide paint (Captain AF Kuroshio Ichiban (1 liquid type) manufactured by Kansai Paint Co., Ltd.) was used as a NK 2 force pump with Xylene. After diluting to a viscosity of 15 seconds, apply it to a conversion-treated aluminum plate (one that had been subjected to the same undercoating process as in Example 1) as in Example 1 and tested. A painted plate was prepared. In the same manner as in Example 1, the test coated plate was examined for the degree of hydrophilicity of the coating film, the anti-bioadhesive property, the bioremovability, and the environmental impact. The results are shown in Table 17.
  • an oil-releasing silicone resin coating (Nyoclean DX (one-pack type) manufactured by Chugoku Paint Co., Ltd.) is applied to NK 2 with Xylene. Diluted to a viscosity of 15 seconds, and treated as in Example 1 with a chemically treated aluminum plate (the same as in Example 1 but with the special intermediate coating Sylbex applied after undercoating). ) To prepare a test coated plate. In the same manner as in Example 1, the test coated plate was examined for the degree of hydrophilicity of the coating film, the ability to prevent bioadhesion, the ability to remove the living body, and the degree of environmental impact. The results are shown in Table 17.
  • a general-purpose hard vinyl chloride resin sheet (thickness: 2 mm) was used as a test sample, and this sheet was treated in the same manner as in Example 1 to prevent the coating from becoming hydrophilic and prevent bio-adhesion. , Bioremovability and environmental impact were examined. The results are shown in Table 17. Coating parent
  • test painted plate (150mm X 400mm) prepared in Example 2 was suspended in a model waterway (average tidal velocity of 20cmZ seconds) with almost constant flow velocity of seawater on the coastal area of Himeji, Hyogo, Japan. They were then immersed and examined for their ability to prevent and adhere to living organisms in a real marine environment, their ability to remove living organisms, and their environmental impact.
  • the test was started in spring, when the activity period of Fujibo began, and was measured at 12, 24 and 42 months after the start of the test. Table 18 shows the results.
  • the evaluation method for each test is the same as in Example 1.
  • Example 73 Using the coated plates prepared in Examples and Comparative Examples shown in Tables 18 and 19, in the same manner as in Example 73, the anti-bioadhesive property, bio-removability and bio-removal property in a real marine environment were used The environmental impact was investigated at 12 months, 24 months and 42 months after the start of the test, respectively. The results are shown in Tables 18 and 19.
  • test painted plate (150mm x 300mm) prepared in Example 2 was attached to the submerged area below the draft line of a ship with a displacement of 50 tons, and berthing and sailing were performed under the following conditions. After returning, the bioadhesion-preventing property was examined every 12 cycles, 24 cycles, and 36 cycles. After 36 cycles, the bioremovability was examined. The tests begin in the spring, when the activity period of FUJIPPO begins, and the evaluation method for each test is the same as in Example 1. Table 20 shows the results.
  • Example 121 A composition (Example 121) in which the composition of Example 1 was blended with 1 PHR of NetKing 300 manufactured by Keiei Kasei Co., Ltd. as a diatom adhesion inhibitor (Example 121), a biological repellent and Then, a composition (Example 122) containing 1 PHR of Baydan GPA manufactured by Keiei Kasei Co., Ltd. was produced, and placed in a model channel under the same conditions as in Example 73. The marine environment test was conducted for 54 power months, and observations were made of Fujipo and diatom deposits. Table 22 shows the results.
  • the resin (b) is silicone resin (one-pack type antibacterial sealant X31-1667 manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd .; hereinafter, "silicone resin (:)").
  • the compound A was added as a hydrolyzable group-containing organometallic compound (a) at 1.5 PHR, and the surface conditioner F was added at 0.015 PHR (mixed composition).
  • the resin composition is shown in Table 23.)
  • the resin composition was cast on an aluminum plate treated with AM-712 at 10 mil. After drying at room temperature for 7 days, a coated plate (dry film thickness: about ⁇ ! Was prepared.The coated plate was stored in a constant temperature / humidity (35, 95% R ⁇ ) bath for 20 hours. Was made hydrophilic and used as a test coated plate (three sheets were prepared).
  • LDL low-density lipoprotein
  • ion-exchanged water ion-exchanged water
  • HOMOSPA manufactured by Tokushu Kika Kogyo Co., Ltd.
  • test coated plate is vertically placed in the aqueous LDL dispersion (a) and the aqueous cholesterol dispersion (b) at 37, respectively, which are stirred in a glass container. After holding for 24 hours, the removed coated plate was dried with a 37 for 16 hours, and then the adhesion of LDL and cholesterol on the surface was examined with an electron microscope. Due to They were observed and evaluated according to the following criteria.
  • Adhesion area is less than 1 to 10 in the microscope field of view
  • Attachment area is 110 ⁇ in the microscope field of view: I 3
  • the coated plate subjected to the adhesion test was washed by spraying 3000 ml of ion-exchanged water (washing water was collected in a beaker), and the coated plate surface after water washing was evaluated in the same manner as above by an electron microscope. . Also, after adjusting the concentration of the washing water in the beaker used for washing so that the detection limit is 0.05 ppm, the atomic absorption spectrum method (Ltd.) The analysis was performed using an atomic absorption spectrum measuring instrument HI TACHI Z-5500 manufactured by Hitachi, Ltd.). The higher the detection amount, the better the removability.
  • Table 24 shows the results of the above tests.
  • silicone resin (elastic silicone KR_2038 manufactured by Shin-Etsu Chemical Co., Ltd.), hereinafter referred to as “silicone resin DJ” and a curing agent ( Shin-Etsu Chemical Co., Ltd.'s D2038) was mixed, and Compound A was added as a water-decomposable group-containing organometallic compound (a) with 1.5 PHR, and surface conditioner F was added.
  • the mixed composition is shown in Table 25.
  • This resin composition was diluted with mineral spirits to a concentration of 20%, and the mixture was mixed with Shin-Etsu Chemical Co., Ltd. Silicone resin tube manufactured by Co., Ltd.
  • One end of the tube was immersed, and the other end of the tube was connected to the pump.
  • a polyethylene tube was arranged so that the dispersion from the pump returned to the glass container.
  • the dispersions (a) and (b) were circulated for 120 hours at a discharge pressure of 0.3 MPa. After stopping the pump, the tube was removed, dried at 37 for 16 hours, and a tube with an inner surface treated with a physiological substance was prepared (three tubes).
  • Example 123 A part of this processing tube was cut, and the same as in Example 123 was cut. Then, observation and evaluation were performed using an electron microscope.

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Abstract

L'invention se rapporte à une composition de résine permettant d'empêcher la fixation d'organismes aquatiques ou de substances physiologiques et comportant un composé métallique organique hydrolysable susceptible de conférer une caractéristique d'hydrophilie à une surface, et une résine utilisée comme liant. L'invention se rapporte à une composition, à une structure et à un élément médical préparés à l'aide de ladite composition de résine, qui sont capables d'empêcher la fixation d'un organisme aquatique, d'une substance physiologique et d'une tache hydrophobe et qui s'avèrent également faciles à détacher.
PCT/JP2001/001058 2000-02-21 2001-02-15 Composition de resine permettant d'empecher la fixation d'organismes aquatiques ou de substances physiologiques WO2001060923A1 (fr)

Priority Applications (1)

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AU2001232295A AU2001232295A1 (en) 2000-02-21 2001-02-15 Resin composition for preventing attachment of aquatic organism or physiologicalsubstance

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JP2000-43413 2000-02-21
JP2000043413 2000-02-21

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007517557A (ja) * 2004-01-09 2007-07-05 バイオ−ゲイト アーゲー 創傷被覆材
JP2007520588A (ja) * 2003-12-05 2007-07-26 バイオシグナル リミテッド 抗微生物性化合物と表面およびポリマーとの結合
JP2008144020A (ja) * 2006-12-08 2008-06-26 Chugoku Marine Paints Ltd 積層防汚塗膜、基材の防汚方法、積層防汚塗膜付き基材およびプライマー組成物
WO2008090812A1 (fr) * 2007-01-23 2008-07-31 Daikin Industries, Ltd. Composition de revêtement
JP2012214739A (ja) * 2011-03-28 2012-11-08 Daikin Industries Ltd 水生生物付着防止シート及び水生生物付着防止塗料
WO2015060129A1 (fr) * 2013-10-21 2015-04-30 住友ゴム工業株式会社 Dispositif médical métallique ayant une lubricité et des caractéristiques de faible adsorption de protéines et/ou des caractéristiques de faible adsorption de cellules, et son procédé de production
WO2018182023A1 (fr) * 2017-03-31 2018-10-04 日東電工株式会社 Composition pour formation de film de revêtement, film de revêtement, et feuille adhésive
US10092680B2 (en) 2014-09-02 2018-10-09 Sumitomo Rubber Industries, Ltd. Metal medical device
US10647829B2 (en) 2013-06-20 2020-05-12 Sumitomo Rubber Industries, Ltd. Surface modification method and surface modification body
US10759918B2 (en) 2015-08-03 2020-09-01 Sumitomo Rubber Industries, Ltd. Surface modification method and surface-modified elastic body
JPWO2019139171A1 (ja) * 2018-01-12 2021-01-14 日東電工株式会社 水生生物付着防止用フィルム
JPWO2019139170A1 (ja) * 2018-01-12 2021-01-14 日東電工株式会社 水没型センサーユニット
KR102229068B1 (ko) * 2020-06-01 2021-03-19 주식회사 도민기업 포장용 다층 항균필름

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03259965A (ja) * 1990-03-09 1991-11-20 Nippon Paint Co Ltd 海生生物付着保護上塗塗料組成物
JPH06247816A (ja) * 1993-02-19 1994-09-06 Kanebo Ltd 変色作用の少ない抗菌性ゼオライトの製造法
JPH06322294A (ja) * 1993-05-07 1994-11-22 Shin Etsu Chem Co Ltd 防汚塗料
JPH1088037A (ja) * 1996-09-11 1998-04-07 Nitsuhan Kenkyusho:Kk 非粘着性コーティング用組成物およびコーティング方法
JPH10219190A (ja) * 1997-02-06 1998-08-18 Kansai Paint Co Ltd 多液型水性塗料組成物
JPH11322770A (ja) * 1998-05-07 1999-11-24 Bioshield Technol Inc 水安定化オルガノシラン化合物及びそれを用いる方法
JPH11343462A (ja) * 1998-04-01 1999-12-14 Kansai Paint Co Ltd 水性塗料組成物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03259965A (ja) * 1990-03-09 1991-11-20 Nippon Paint Co Ltd 海生生物付着保護上塗塗料組成物
JPH06247816A (ja) * 1993-02-19 1994-09-06 Kanebo Ltd 変色作用の少ない抗菌性ゼオライトの製造法
JPH06322294A (ja) * 1993-05-07 1994-11-22 Shin Etsu Chem Co Ltd 防汚塗料
JPH1088037A (ja) * 1996-09-11 1998-04-07 Nitsuhan Kenkyusho:Kk 非粘着性コーティング用組成物およびコーティング方法
JPH10219190A (ja) * 1997-02-06 1998-08-18 Kansai Paint Co Ltd 多液型水性塗料組成物
JPH11343462A (ja) * 1998-04-01 1999-12-14 Kansai Paint Co Ltd 水性塗料組成物
JPH11322770A (ja) * 1998-05-07 1999-11-24 Bioshield Technol Inc 水安定化オルガノシラン化合物及びそれを用いる方法

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007520588A (ja) * 2003-12-05 2007-07-26 バイオシグナル リミテッド 抗微生物性化合物と表面およびポリマーとの結合
JP4657222B2 (ja) * 2004-01-09 2011-03-23 バイオ−ゲイト アーゲー 創傷被覆材
JP2007517557A (ja) * 2004-01-09 2007-07-05 バイオ−ゲイト アーゲー 創傷被覆材
JP2008144020A (ja) * 2006-12-08 2008-06-26 Chugoku Marine Paints Ltd 積層防汚塗膜、基材の防汚方法、積層防汚塗膜付き基材およびプライマー組成物
US9175177B2 (en) 2007-01-23 2015-11-03 Daikin Industries, Ltd. Coating composition
WO2008090812A1 (fr) * 2007-01-23 2008-07-31 Daikin Industries, Ltd. Composition de revêtement
JPWO2008090812A1 (ja) * 2007-01-23 2010-05-20 ダイキン工業株式会社 塗料組成物
KR101035460B1 (ko) 2007-01-23 2011-05-18 다우 코닝 코포레이션 도료 조성물
AU2008208419B2 (en) * 2007-01-23 2012-02-02 Daikin Industries, Ltd. Coating composition
JP5315063B2 (ja) * 2007-01-23 2013-10-16 ダイキン工業株式会社 塗料組成物
JP2012214739A (ja) * 2011-03-28 2012-11-08 Daikin Industries Ltd 水生生物付着防止シート及び水生生物付着防止塗料
US10647829B2 (en) 2013-06-20 2020-05-12 Sumitomo Rubber Industries, Ltd. Surface modification method and surface modification body
JP2015107312A (ja) * 2013-10-21 2015-06-11 住友ゴム工業株式会社 潤滑性、低タンパク質吸着性および／または低細胞吸着性を有する金属医療用具及びその製造方法
WO2015060129A1 (fr) * 2013-10-21 2015-04-30 住友ゴム工業株式会社 Dispositif médical métallique ayant une lubricité et des caractéristiques de faible adsorption de protéines et/ou des caractéristiques de faible adsorption de cellules, et son procédé de production
US10092680B2 (en) 2014-09-02 2018-10-09 Sumitomo Rubber Industries, Ltd. Metal medical device
US10759918B2 (en) 2015-08-03 2020-09-01 Sumitomo Rubber Industries, Ltd. Surface modification method and surface-modified elastic body
WO2018182023A1 (fr) * 2017-03-31 2018-10-04 日東電工株式会社 Composition pour formation de film de revêtement, film de revêtement, et feuille adhésive
JPWO2019139171A1 (ja) * 2018-01-12 2021-01-14 日東電工株式会社 水生生物付着防止用フィルム
JPWO2019139170A1 (ja) * 2018-01-12 2021-01-14 日東電工株式会社 水没型センサーユニット
JP7416627B2 (ja) 2018-01-12 2024-01-17 日東電工株式会社 水生生物付着防止用フィルム
JP7426236B2 (ja) 2018-01-12 2024-02-01 日東電工株式会社 水没型センサーユニット
US11964740B2 (en) 2018-01-12 2024-04-23 Nitto Denko Corporation Submersible sensor unit
KR102229068B1 (ko) * 2020-06-01 2021-03-19 주식회사 도민기업 포장용 다층 항균필름

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