WO1992020747A1 - Compositions marines comportant de preference des domaines concentres d'agents organo anti-fouling exempts d'etain - Google Patents

Compositions marines comportant de preference des domaines concentres d'agents organo anti-fouling exempts d'etain Download PDF

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Publication number
WO1992020747A1
WO1992020747A1 PCT/US1992/004077 US9204077W WO9220747A1 WO 1992020747 A1 WO1992020747 A1 WO 1992020747A1 US 9204077 W US9204077 W US 9204077W WO 9220747 A1 WO9220747 A1 WO 9220747A1
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WIPO (PCT)
Prior art keywords
dimethyl
acid
chloro
methyl
chlorophenyl
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PCT/US1992/004077
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English (en)
Inventor
Vincent D. Mcginniss
Richard J. Dick
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Battelle Memorial Institute
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Application filed by Battelle Memorial Institute filed Critical Battelle Memorial Institute
Priority to AU19235/92A priority Critical patent/AU660030B2/en
Priority to JP4510674A priority patent/JPH06507661A/ja
Publication of WO1992020747A1 publication Critical patent/WO1992020747A1/fr

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    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic

Definitions

  • the present invention relates to anti-fouling marine coatings and mor particularly to novel low toxicity anti-fouling agents therefor.
  • One of the earliest need for performance-oriented coatings was in the marine environment. Early formulation were designed around known toxins, such as copper and mercury compounds
  • anti-fouling compound based on copper and tin commonly are incorporated into somewhat water- sensitiv binders to afford gradual break-down of the film to permit a sustained release of th "poison". This required self-erosion property necessitates frequent repainting of shi bottoms, depending upon location and severity of exposure conditions.
  • Today's anti-fouling coatings use two general leaching mechanisms, dependin on the type of resin matrix selected, soluble or insoluble.
  • the insoluble-matrix typ leaves a resinous skeleton intact as the toxicant particles are removed by dissolving int solution in seawater.
  • This also is called the contact type because it depends upon th toxicant migrating to the surface and entering solution by making contact with seawate Since the resins are somewhat water-permeable, the toxic particles may diffuse throug the semi-permeable coating, and as one particle dissolves, another is exposed t seawater.
  • the contact type contains several times more toxicant than the soluble type The resulting thicker films of toxicant provide a longer service life to the anti-foulin topcoats.
  • the insoluble-matrix type of paint does not contain a extended pigment, and the geometry of the dry film requires high toxicant loadings (52 to 74% by volume) to ensure the G12O particles will be in continuous contact with eac other. Below the level of cubic packing (52%), the resin will encase the CU2O particle and prevent solution; above the level of hexagonal packing (74%), the coating will b too resin-poor to maintain film integrity.
  • These figures may vary somewhat in actua practice, and it is common to adjust the leaching rate and the effective range of toxican loading (e.g. by the addition of rosin or other natural resins). In common practice, bot natural resins and extender pigments are frequently used.
  • Pr proposals include, for example, Japanese Patents 56156202 and 52117425 report use of a combination of a napthoquinone and a thiuram disulphide in order to obtain a fouling activity, while Japanese Patent 63243067 proposes the use of diphenylamin Despite these proposals, there still is a substantial need in the anti-fouling arena for ne low toxicity anti-fouling coatings, caulks, and the like.
  • the present invention is addressed to a curable, marine anti-fouling compositi of a thermoplastic or thermosetting binder, solvent, non-tin, organb anti-fouling age and optionally conventional additives, e.g. leaching agents, opacifying pigments, e
  • the anti-fouling agents are found in preferentially-concentrated domains (hereinaft often referred to as "PCD" or "PCDs”) in the cured compositions.
  • PCD preferentially-concentrated domains
  • the PCDs can termed non-homogeneous, phase-separated, or incompatible in the system.
  • the art te used in describing the PCDs of anti-fouling agents is not limitative of the invention the disclosure herein will demonstate.
  • PCDs are created by forming oligomeric adduct of the anti-fouling agent which adduct is formed into PCDs upon t curing of the composition. Additional techniques for forming PCDs of anti-fouli agent will be revealed herein.
  • the present invention also is addressed to the use of new, low toxicity an fouling agents which comprise pesticide or herbicide compounds having a ⁇ value between about 0.01 and 3, a Z value for vinyl or aromatic compounds of between abo 0.01 and 0.08, and an LD50 value of greater than 200 mg/kg against rats or mice.
  • Su pesticide or algicide compounds broadly can be selected from heterocyclic compound aromatic compounds substituted with heteroatom substituents, various ami compounds, carbocyclic vinyl ether ketones, certain phospho compounds, certai polychlorinated carbocyclic and acyclic compounds, certain chlorinated carbocycl carboxylates, antimony tartrate, boric acid, and cupric oleate.
  • Exemplary aromat compounds include diaromatic compounds linked with a sigma bond or with a carbon heteroatom linkage, fused aromatic rings, and mono-aromatic compounds.
  • Advantages of the present invention include the ability to formulate marine an fouling compositions which contain low toxicity anti-fouling agents.
  • Another advantag is the ability to formulate marine anti-fouling coating compositions wherein the lo toxicity anti-fouling agents display improved effectiveness by virtue of being formed i PCDs.
  • Fig. 1 is a scanning electron micrograph (SEM) at 10,000 X of the cured epo resin composition of Example 16 containing an organo toxicant freely-dispersed therei
  • Fig. 2 is an SEM at 10,000 X of a cured epoxy resin composition of Example containing the same organo toxicant free-dispersed therein and a domain-formi polysulfide polymer
  • Fig. 3 is a pictorial representation of the SEM results of Fig. 2, where A is t discontinuous polysulfide/chlorine compound environment and B is the continuo polysulfide chlorine compound environment;
  • Fig. 4 is an SEM at 250 X of a cured epoxy resin composition of Example containing a polymer of the same organo toxicant and the polysulfide polymer of Fig. which product forms discrete domains;
  • Fig. 5 is an Energy Dispersion Spectroscopy analysis for the chlorine content the organo toxicant polymer domains of Fig.4;
  • Fig. 6 is an Energy Dispersion Spectroscopy analysis for the sulfur content the organo toxicant polymer domains of Fig. 4;
  • Figs. 7 and 8 are SEMs at 500 X and 2,500 X, respectively, showing t domain structures formed in a continuous PVC binder by the domain creating acry polymers and organo toxicant monomer described in Example 17;
  • Fig. 9 is an optical micrograph (SEM) at 1,500 X of the sample of Figs.7 and Fig. 10 is an Energy Dispersion Spectroscopy analysis at 1,500 X for t oxygen content of the sample of Figs.7-9;
  • Fig. 11 is an optical micrograph at 2,000 X of the sample of Figs.7 and 8;
  • Fig. 12 is an Energy Dispersion Spectroscopy analysis at 2,000 X for t oxygen content of the sample of Figs.7-9;
  • Fig. 13 is an optical micrograph at 200 X showing the domain structures form in a continuous epoxy resin by LP-32 polysulfide resin of Example 18;
  • Figs. 14-15 are Energy Dispersion Spectroscopy maps at 200 X for chlorine a sulfur, respectively, of the resin system of Fig. 13. Detailed Description of the Invention
  • organo-tin anti-fouling agents due their human toxicity characteristics, the art truly needs to enable anti-fouling agen which exhibit low human toxicity characteristics. Once such agents are identified, th must be compatible with remaining formulation ingredients in marine coatings and oth marine compositions. Also, these low toxicity anti-fouling agents must display effica characteristics making them practical. Use of the non-tin, organo anti-fouling agents in marine composition will provide a modicum of protection to the substrate to which t composition is applied, yet enhanced, long-term protection is desired. Unexpectedly, was discovered that enhanced activity for extended periods of time could be achieved controlling the physical form in which the anti-fouling agents were presented in t cured marine compositions.
  • Phase separation was the term initially used to define suc physical form. Later, the term “preferentially-concentrated domains” was adopted due the variety of techniques developed for achieving the desired physical form of the an fouling agents. Thus, islands, pools, or domains where the anti-fouling agen concentrate are created in the cured composition. Such domains typically will be the si of from about 0.3 ⁇ to 500 ⁇ (micrometers).
  • the anti-fouling agent could complex o otherwise associate with a compound incompatible with the continuous phase of th composition. So long as PCDs of the anti-fouling agent are formed in the cure composition, the precepts of the present invention have been practiced.
  • non-tin, organo anti-fouling agents may be used in the presen invention for forming PCDs thereof.
  • the preferred non-tin anti-fouling agents useful i the present invention broadly are selected from compounds which hav exhibited terrestrial biologic activity, e.g. known herbicides and pesticides.
  • herbicides are to be interpreted broadly as including not only compound which selectively and/or broadly kill various plant life, but also include various plan growth regulators, algicides, and the like.
  • Pesticides, for present purposes also shoul be broadly interpreted as compounds which are selectively and/or broadly toxic t harmful plant infestations, such as acaricides. These compounds, however, mu exhibit low toxicity to humans.
  • "low toxicity to humans" i determined when the LD50 value is greater than 200 mg/kg against rats or mice.
  • ⁇ factor is base upon the McGinniss predictive relationship as defined in Organic Coatings in Piasti Chemistry,. Vols. 39 and 46, pp 529-534 and 214-223, respectively (1978 and 198 respectively).
  • the McGinniss predictive relationship defines the ⁇ factor as a weig fraction of heteroatoms contained in the monomer or in the monomer repeat unit of a oligomer or polymer.
  • the McGinniss predictive relationship defines the Z parameter a the weight fraction of ⁇ electrons contained in the monomer or in the monomer repe unit of an oligomer or polymer (e.g. ⁇ electron density of aromatic or viny compounds).
  • Biologically-active compounds that possess a ⁇ facto and Z parameter within the ranges defined herein, and possess the requisite LD50 valu will be compounds which display anti-fouling characteristics in marine coatings.
  • the foregoing biologically active compound display efficacy as anti-fouling agents. Their diminished toxicity to humans is a decide benefit compared to conventional organo-tin anti-fouling agents.
  • the low toxicity anti-fouling agents of the present invention can described as biologically active terrestrial compounds (e.g. pesticides and herbicide that are heterocyclic, aromatic with heteroatomic substituents, amino compounds, an carbocyclic ketone vinyl ethers.
  • the aromatic compounds can be further identified mono-aromatic, fused aromatic ring compounds, and diaromatic compounds linked wit a sigma bond or with a carbon or divalent heteroatomic substituent.
  • hetero-substituted aliphatic compounds that are biologically active an possess the requisite ⁇ value and Z parameter also may find use as anti-fouling agents i accordance with the precepts of the present invention.
  • compounds whic do not quite fit any of the foregoing definitions also should be recognized as include within the scope of the anti-fouling agents of the present invention. These include bori acid which has been demonstrated to be quite active as an anti-fouling agent, as the dat will testify. Additional compounds include, for example, antimony tartrate and cupri oleate.
  • additional low toxicity antifouling agents/reactants of the prese invention include those set forth in Table 2 below.
  • Additional candidate low toxicity anti-fouling agents include:
  • 6-chloropiperonyl chrysanthemumate N-butyl-N-ethyl- ⁇ , ⁇ , ⁇ -trifluoro-2-6-dinitro-p-toluidine bis (p-chlorophenyl)-3-pyridine methanol bis (dialkylphosphinothioyl) disulfide bis (4-hydroxyiminomethyl pyridinum-1 -methyl) ether dichloride 2,4-bis (3-methoxylpropyla ⁇ rdno)-6-methylthio-S-triazine bis (pentachloro-2,4-cyclopentadien- 1-yl) boric acid
  • N-trichloromethylthio-benzothiazolone N-trichloromethylthiobenzoxazolone 2 ⁇ ,2-tricWoro-n- ⁇ entacUoro-phenyl)acetimidoyl chloride 2-(2,4,5-trichlorophenoxy)ethyl sulfate, sodium salt N,N'-N"-trichloro-2,4,6-triamine-l,3,5-triazine 2- ⁇ jUoro-4-(di-emylarnino)-6-(emyla ⁇ mo)-s-triazine tert-butyl 4(or 5)-chloro-2-methylcyclohexanecarboxylate S-propyldipropylthiocarbamate zinc ethylene bisdithiocarbamate zinc dimethyldithiocarbamate 3,5-dinitro-o-toluamide.
  • Linking of the anti-fouling agent with an oligomer or polymer can accomplished by a variety techniques, depending upon the available functionality of t anti-fouling agent.
  • ethylenic unsaturation in the anti-fouling agent can copolymerized with acrylate or other ethylenically unsaturated monomers in conventio fashion. See, for example, Acrylic Monomer, product literature, Dow Badisc Company, Form No. A-GB-101; Preparation, Properties and Uses of Acrylic Polyme product liturature, Rohm and Haas Company, Form CM-19 B/eh; and U.S. Pat.
  • Anti-fouling agents with reactive hydroxyl or other active hydrogen functionality can be reacted with a polyisocyanate for forming an an fouling agent adduct.
  • reactive hydroxyl or other active hydrogen functionality e.g NH, -NH2, -SH, or the like
  • a polyisocyanate for forming an an fouling agent adduct.
  • Additional techniques for forming PCDs include, for example, complexi (association or other mechanism) of the anti-fouling agent with another ingredient in t formulation, e.g., pigment, polymer or oligomer additive, or the like.
  • Anoth technique involves the anti-fouling agent being relatively more miscible in discontinuous phase (or particles), than in the continuous phase of the coating. Agai PCDs would be formed. Regardless or the technique, so long as PCDs of the an fouling agent are formed in the fianl product, improved long-term anti-fouling activi will be expressed by the anti-fouling agents.
  • the formulation of the marine compositions containing the anti-fouling agents the present invention is practiced in conventional fashion as those skilled in the a appreciate utilizing conventional film-forming binders appropriate for mari environments.
  • Marine compositions broadly for present purposes include, for examp coatings, elastomers, sealants, caulks, grouts, concretes, and like polymeric structu appropriate for the marine environment
  • the form of the marine composition can be a coating, as rigid or elastomeric (including foamaceous) objects, as a sealant or a three-dimensional configured structure such as villous trailing fingers in the exterior marine vessels.
  • Conventional additives, organic solvents (including reactive solvents diluents), and the like are incorporated into the formulation.
  • the proportion of a fouling agent generally is between about 1 and 20 weight percent by weight of t formulation.
  • EXAMPLE 1 In order to bind an organic anti-fouling agent into a polymeric structure, a thr neck reaction flask fitted with a mechanical stirrer, thermometer, and reflux conden was charged with a polysulfide polymer (200 g of LP-3 polysulfide polymer, Thioko 1,2-dicyano, tetrachlorobenzene (100 g of Nopocide brand, Diamond Shamroc potassium hydroxide (80 g), and dimethyl sulfoxide (100 ml). The reaction mixture heated for three hours to a temperature of 105° C, cooled to room temperature, wash and subjected to vacuum for removal of solvent.
  • the resulting polymeric struct 45701-1 can be represented conventionally as follows:
  • An anti-fouling agent-modified adduct was synthesized in accordance with t following reaction scheme. Toluene (100 ml) was added to a roundbottomed fla followed by the addition of hydroxyethyl methacrylate (14 ml) and toluene diisocyan (17 ml). This mixture was stirred for one hour at room temperature followed by addition of triethylamine catalyst (three drops). After two hours, 3,4-dichloroanal (16 ml) was added to the solution which then was heated to 50° C and held for 10 ho The resulting solid product was filtered through number 40 filter paper and washed additional alliquots of toluene and hexane. Infrared analysis showed the expec urethane-amide structures consistent with the desired reaction product 45701-3 whic illustrated conventionally below.
  • EXAMPLE 3 A pressure reactor fitted with a pressure gauge was loaded with 3-(3, dichlorophenyl)- 1,1 -dimethyl urea (45 g) and propylene oxide (150 ml). The react was sealed and heated to 80° C (a pressure reading of 50 psi) and held for 20 hou The sample removed from the reactor was analyzed by IR and showed broadening of t NH bands and the presence of hydroxyl functionality and some polyether functionali (1100 cm'l). Preparation of this material is similar to that preparation described in Polymer Science, vol. 15, 427-446 (1955). Reaction production 45701-4 can represented conventionally below. It will be observed that the reaction product contai a hydroxyl group which could be reacted with isocyanate or other functionality for incorporation into a curable resin.
  • reaction product 45701-5 which can be represent conventionally as follows:
  • Polymeric structur 45701-10 was prepared by adding DER 331 resin (11 g) to 2-mercaptobenzothiazole (1 g) dissolved in toluene solvent (35 ml). This reaction mixture was heated to 90" C three hours until a clear solution was obtained.
  • the second polymeric structu identified as 45701-11 was prepared by the same reaction procedure utilizing morpholi in place of 2-mercaptobenzothiazole. Both structures can be represented conventional below:
  • Test panels were 15.24 cm x 30.48 cm (6 in x 12 in) in dimension and we constructed of a white plastic top surface and a black plastic bottom surface.
  • the te panels were coated on both sides with the two formulations above-tabulated at a fil thickness of about 5 mils dry.
  • the test panels then were exposed horizontally with t white surface upward and the black surface downward in the ocean at Daytona Beac Florida, U.S.A.
  • a control panel consisted of 12 wt-% triphenyl tin hydroxide dispers in a resinous vinyl binder (80 wt-parts of a vinyl chloride polymer, VAGH bran Union Carbide Corporation, New York, New York) reduced in methyl ethyl keto solvent to 50% solids content The following results were recorded.
  • Example 11 The Control Paint of Example 10 was formulated with additional polymeric a as-is anti-fouling additives and evaluated as in Example 10, with the following resul being recorded: TABLE?
  • EXAMPLE 12 The Control Paint of Example 10 was formulated with additional anti-fouling additives and evaluated with the following results being recorded: TABLE 4 gample Rating After Exposure" (Additive at 20 wt-%) 4 Months
  • Example 10 again was formulated with additional anti fouling additives and evaluated as above with the following results being recorded: TABLE 5 Sample Rating After Exposure* (Additive at 20 wt-%) 1 Month 4 Months
  • EXAMPLE 16 An epoxy resin system was examined for its ability to be modified so as t preferentially influence the concentration or location of an anti-fouling agent (No ocid N-96 , see Example 1) within its structure. A direct comparison was made between epoxy resin (EPON 828 epoxy resin, diglycidyl ether of bis-phenol A, Shell Chemic Company) and the same epoxy resin containing a domain structuring polymeric materi such as a polysulfide resin (LP-32 polysulfide resin, Thiokol Corporation). Bo systems contained the same anti-fouling agent The compositions formulated are s forth below:
  • Sample 1 that contained only the hexachlorophene anti-fouling agent and not t domain creating polymer (LP-32 polysulfide), provided an even chlorine distributio throughout the surface of the sample. Sample 1 also showed no regular domain si structure present as can be seen by reference to Fig. 1. Sample 2, however, exhibited very unique regular domain size (less than 1 ⁇ ) structure or pattern which was created the LP-32 polysulfide polymer (see Fig. 2).
  • Sample 3 contained larger dom size structures (about 100 ⁇ ), and chlorine from the Nopocide was found only in t areas where the domain or island was located. Areas between the islands did not cont chlorine.
  • a chlorine or sulfur density map of the sample surface follows the outline the domain structure (see Figs.4, 5, and 6).
  • EXAMPLE 17 an unreacted toxicant was evaluated with respect to its ability preferentially concentrate in domains of another material created within a continuo polymeric binder or carier.
  • a continuo polymeric binder or carier For example, certain types of acrylic copolymers dispers in a polyvinyl chloride (PVC) polymer can create discrete domains wherein a toxica molecule can preferentially concentrate.
  • PVC polyvinyl chloride
  • the toxicant was the 3, dichloroanaline-based acrylate monomer of Example 2 (80 wt-% concentration, sha melting point at 180° C)
  • the continuous phase was VAGH PVC polymer (see Examp 10)
  • the domain-creating polymer was a mixture of polyhydroxyethylmethacryla (10 wf-% concentration, melting point less than 250° C) and a polymer of a methacryl acid ester of an amino carbamate monomer (10 wt-% concentration, melting point great than 300° C).
  • Example 18 Sample 2 of Example 16 was prepared again, except that the hexachlorophen toxicant-was replaced by Nopocide N-96. Thus, a blend of domain-forming LP-3 polysulfide resin and the Nopocide is being evaluated with respect to the formation o PCDs of Nopocide.
  • the cured epoxy resin system was subjected to SEM and E analysis with the results set forth at Figs. 13-15.
  • Fig. 13 is the SEM micrograph of an area of the cured epoxy resin at 200 X. is evident that the LP-32 polysulfide polymer created discrete domains.
  • Fig. 14 displa the EDS analysis of chlorine at 200 X, while Fig. 15 is for sulfur.
  • a comparison of t two EDS maps reveals that chlorine and sulfur both are present at the same location the cured epoxy resin system. Chlorine comes from the Nopocide toxicant, while sul comes from the LP-32 polysulfide resin.
  • the formation of PCDs of no tin, organo anti-fouling agents is seen to have been achieved.
  • such formation due to the preferential formation of domains by the LP-32 polysulfide polymer with t concomitant preferential concentration of the toxicant with the polysulfide polymer.

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  • Engineering & Computer Science (AREA)
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Abstract

Composition marine polymérisable anti-fouling comprenant un agent liant thermoplastique ou thermodurcissable, un solvant, un agent organo anti-fouling exempt d'étain et éventuellement des additifs conventionnels, par ex. des agents de lessivage, des pigments opacifiants, etc. Lesdits agents anti-fouling sont présents dans des domaines préférentiellement concentrés (ci-après nommés ''PCD'') dans lesdites compositions polymérisées. Les PCD peuvent être qualifiés de non homogènes, séparés en phase ou incompatibles dans le système. Le terme spécialisé utilisé pour décrire les PCD d'agent anti-fouling n'est pas limitatif pour la présente invention, comme cette dernière le démontre. De préférence, on crée des PCD en formant un produit d'addition oligomère de l'agent anti-fouling, ledit produit d'addition étant formé en PCD lors de la polymérisation de ladite composition. Des techniques supplémentaires de formation de PCD d'agent anti-fouling sont également décrites. La présente invention concerne en outre de nouveaux agents anti-fouling, à faible toxicité qui contiennent des composés pesticides ou herbicides ayant un facteur ψ situé entre environ 0,01 et 3, une valeur Z pour les composés vinyles ou aromatiques située entre environ 0,01 et 0,08 et une valeur LD50 supérieure à 200 mg/kg contre les rats ou les souris. Lesdits composés pesticides ou algicides peuvent être sélectionnés en gros parmi des composés hétérocycliques, des composés aromatiques substitués par des substituants hétéroatomiques, divers composés amino, des cétones d'éther de vinyle carbocycliques, certains composés phospho, certains composés acycliques et carbocycliques polychlorés, certains carboxylates carbocycliques chlorés, du tartrate d'antimoine, de l'acide borique et de l'oléate cuivrique.
PCT/US1992/004077 1991-05-17 1992-05-14 Compositions marines comportant de preference des domaines concentres d'agents organo anti-fouling exempts d'etain WO1992020747A1 (fr)

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AU19235/92A AU660030B2 (en) 1991-05-17 1992-05-14 Marine compositions bearing preferentially concentrated domains of non-tin, organo or inorganic anti-fouling agents
JP4510674A JPH06507661A (ja) 1991-05-17 1992-05-14 錫を含有しない有機汚れ止め剤の選択的濃縮領域を有する船用組成物

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US702,241 1991-05-17

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WO1995011592A1 (fr) * 1993-10-29 1995-05-04 J.C. Hempel's Skibsfarve-Fabrik A/S Structure marine
WO1995017478A1 (fr) * 1993-12-21 1995-06-29 Bayer Aktiengesellschaft Produit antisalissures
WO2000014058A1 (fr) 1998-09-04 2000-03-16 Asahi Kasei Kabushiki Kaisha Nouveau compose chromo-sensible
WO2001066515A1 (fr) * 2000-03-02 2001-09-13 Asahi Kasei Kabushiki Kaisha Substance chromogene et materiau d'enregistrement
WO2009138950A1 (fr) * 2008-05-12 2009-11-19 Biopaint S.R.L. Nouveaux agents d'adhésion antimicrobiens écologiques destinés à des peintures antisalissures et peintures antisalissures contenant de tels agents
US7635662B2 (en) 1998-09-04 2009-12-22 Chemipro Kasei Kaisha, Ltd. Compound for color-producing composition, and recording material
CN101003499B (zh) * 2000-03-02 2011-01-19 Chemipro化成株式会社 生色组合物和记录材料

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JP5382711B2 (ja) * 2009-09-07 2014-01-08 国立大学法人北陸先端科学技術大学院大学 光照射によって誘電率が変化する膜を用いた電子デバイス
JP7437026B2 (ja) * 2020-04-23 2024-02-22 国立大学法人東京工業大学 メカノラジカル検出又は測定方法

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FR2648676A1 (fr) * 1989-06-22 1990-12-28 Derivery Sa Nouveau compose pour la realisation de resine a proprietes bioactives et procede pour la preparation de ce compose

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FR2332765A1 (fr) * 1975-11-28 1977-06-24 Ventron Corp Composition concentree d'un biocide dans une resine thermoplastique et son utilisation
US4157983A (en) * 1977-07-28 1979-06-12 Champion International Corporation Process for production of encapsulated water-dispersible materials
US4881976A (en) * 1987-11-17 1989-11-21 Rhone-Poulenc Inc. Antifouling paints containing matrices cross-linked with lanthanides and methods of making and use
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FR2648676A1 (fr) * 1989-06-22 1990-12-28 Derivery Sa Nouveau compose pour la realisation de resine a proprietes bioactives et procede pour la preparation de ce compose

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AU701615B2 (en) * 1993-12-21 1999-02-04 Bayer Aktiengesellschaft Anti-fouling compositions
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WO2000014058A1 (fr) 1998-09-04 2000-03-16 Asahi Kasei Kabushiki Kaisha Nouveau compose chromo-sensible
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WO2009138950A1 (fr) * 2008-05-12 2009-11-19 Biopaint S.R.L. Nouveaux agents d'adhésion antimicrobiens écologiques destinés à des peintures antisalissures et peintures antisalissures contenant de tels agents
US8398759B2 (en) 2008-05-12 2013-03-19 Biopaint S.R.L. Environmental friendly anti-microbial adhesion agents for anti-fouling paints and anti-fouling paints containing them
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AU660030B2 (en) 1995-06-08
CA2107207A1 (fr) 1992-11-18
AU1923592A (en) 1992-12-30
JPH06507661A (ja) 1994-09-01
EP0584204A1 (fr) 1994-03-02

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