JP2005255858A - Antifouling resin and method for producing the same, and antifouling coating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an antifouling resin having low toxicity and high antifouling activity. <P>SOLUTION: The antifouling resin comprises a semi-IPN (mutually invadible polymer network) composite comprising at least a silicone resin prepared by polymerizing, using as a monomer, a trialkoxysilane having an ammonium salt structure represented by formula (1) (wherein R<SB>1</SB>, R<SB>2</SB>, R<SB>3</SB>, and R<SB>4</SB>are each an alkyl group; and R<SB>5</SB>is a 1-6C alkyl group) and a radical-polymerizable polymer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an antifouling resin, a method for producing the same, and an antifouling paint, and in particular, an antifouling resin having excellent antifouling property, storage stability and easy use, a method for producing the same, and an antifouling agent. It relates to dirty paint.

  Underwater structures such as ships, marine structures, aquaculture fishing nets, buoys, industrial water systems, etc. are constantly exposed to the water inhabited by marine organisms, so microorganisms such as bacteria adhere over time, Furthermore, marine adhering organisms (for example, animals and plants such as barnacles, mussels, seaweeds, diatoms, etc.) are attached using this as a scaffold.

  When the surface of an underwater structure is covered with these microorganisms, animals and plants, various problems are caused. For example, when the ship's bottom is covered with the above-mentioned organisms, seawater friction resistance increases, and extra energy is required to drive the ship, so the efficiency of the ship's fuel decreases. In the case of fishing nets, clogging occurs, resulting in massive death of seafood. Furthermore, in the case of a buoy, it sinks. In addition, there may be a problem that the covered surface portion is corroded or the work of fishermen is reduced.

  In addition, in industrial water systems that use natural water such as river water and lake water as cooling water, etc., and in circulation cooling devices that use waterworks in the middle, bacteria, diatoms, cyanobacteria, etc. contained in the water propagate, It causes troubles such as a decrease in cooling efficiency due to adhesion to the vessel wall, blockage of water pipes, and a decrease in flow rate.

  As a method for preventing such adhesion of microorganisms and organisms, a method of applying an antifouling paint on the surface of an underwater structure has been conventionally used.

  For example, in recent years, hydrolyzable antifouling paints containing a trialkyltin-containing polymer as an antifouling component have been used. This function is exhibited by the hydrolysis of the trialkyltin-containing polymer in a slightly alkaline atmosphere in water to elute the organotin compound.

  Furthermore, Patent Document 1 discloses an underwater organism adhesion preventing coating composition using a phenol derivative having an alkyl group introduced therein. A phenol derivative having such an alkyl group introduced has a considerably high effect and low toxicity.

  In addition, blending a resin composition obtained by mixing two or more kinds of resins as an antifouling substance has been studied (for example, Patent Document 2).

  On the other hand, as a method of mixing two types of resins, a semi-IPN type complex has been studied. The semi-IPN type composite is a composite having a mutual network intrusion structure as a network polymer and a linear polymer are entangled with each other. Such a semi-IPN type composite has a mutual network intrusion structure, so that a resin physical property that cannot be obtained by a simple mechanical blend of two kinds of resins can be obtained.

Examples of the semi-IPN type composite include those made of a radical polymerization type polymer such as a network silicone resin and a linear vinyl polymer.
JP 3-128302 JP-A-9-279061 “Study on Fisheries”, 1992, Vol. 11, No. 4, p. 71-72

  However, hydrolyzable antifouling paints containing trialkyltin-containing polymers as antifouling components can dissolve highly toxic antifouling agents, killing harmful aquatic organisms, or even impairing their ability to adhere. Since it exhibits antifouling performance, it releases compounds harmful to the living body into the sea, which is a serious problem from the viewpoint of environmental pollution.

  Moreover, when the phenol derivative which introduce | transduced the alkyl group of patent document 1 is used, it is difficult to maintain an antifouling effect for a long period of time, and the device of using together the compound which has water repellency was required.

  Furthermore, there is a problem that a sufficient antifouling property cannot be obtained with a resin in which antifouling substances are mechanically blended like the resin component of Patent Document 2.

  The present invention has been made in view of the above-described conventional problems, and an object of the present invention is to provide an antifouling resin and an antifouling paint having low toxicity and high antifouling activity.

  As a result of intensive studies, the present inventors have found that a polymer containing a trialkoxysilane containing an ammonium salt structure has excellent antifouling properties, and a semi-IPN type complex of this resin and a radical polymerizable polymer is preserved. And found to exhibit physical properties suitable for use.

  That is, the antifouling resin according to the present invention includes at least the general formula (1) in order to solve the above problems.

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents an alkyl group; R ₅ represents an alkyl group having 1 to 18 carbon atoms), at least ammonium It includes a semi-IPN type composite having a silicone resin obtained by polymerizing a trialkoxysilane having a salt structure as a monomer, and a radical polymerizable polymer.

  Here, the semi-IPN (interpenetrating polymer network) type composite is a polymer formed by polymer interpenetrating each other.

  According to this, the silicone resin polymerized by using at least the trialkoxysilane as a monomer in the antifouling resin has effective biorepellency and antibacterial properties.

  Therefore, if this antifouling resin is applied to the one used in the ocean, it prevents the adhesion of marine organisms by preventing the adhesion of microorganisms, and also prevents the adhesion of marine organisms by the adhesion repellent activity. Antifouling effect can be expected. Moreover, if it is used as a material for daily use, it effectively functions as an antibacterial material.

  Further, since this silicone resin further forms a semi-IPN type complex with the radical polymerizable polymer, it has mechanical strength and can be stored well for a long period of time in the state of sol antifouling resin. Furthermore, once solidified, it does not re-disperse in water or an organic solvent, so the risk of elution into water is small. In addition, if the sol-like antifouling resin is diluted, it can be sprayed or applied to the object to which the antifouling effect is desired, and the antifouling property can be easily imparted directly to the object by drying it. Therefore, direct application to various materials such as glass, metal, paper, and plastic becomes possible.

  Here, the semi-IPN type composite is one in which a network polymer and a linear polymer are entangled with each other to form a mutual network penetration structure.

The substituents represented by R _{1 to} R ₅ in the above chemical formula may be the same or different, and some of them may be the same. And some of them may represent different substituents.

  Further, when octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride is used as the trialkoxysilane, good biological repellent properties and antibacterial properties can be imparted.

  Further, when polymethyl methacrylate is used as the radical polymerizable polymer, the antifouling resin can be stored better in a sol state for a long period of time, so that it has excellent storability and the conventional coating method (spraying, Easy to use by casting).

  In addition, the antifouling resin of the present invention can exhibit good biorepellency and antibacterial properties when the trialkoxysilane is contained in the semi-IPN complex in an amount of 60% by weight or more.

  In addition, the said silicone resin has much stronger biological repellent property and antibacterial property by superposing | polymerizing only trialkoxysilane.

  Further, if the silicone resin is obtained by polymerizing the trialkoxysilane and tetraalkoxysilane, the cost can be reduced.

  These antifouling resins are harmless to the human body and the environment, and have biological repellency, antibacterial properties, and antiviral properties, so they can be used as ships, power plants, marine structures, aquaculture fishnets, buoys, and bay harbor paints. Excellent antifouling effect. Alternatively, it can be applied to medical supplies such as contact lenses, door knobs, and antibacterial masks as antibacterial materials.

  Moreover, in order to solve the said subject, the manufacturing method of the antifouling resin of this invention WHEREIN: General formula (1);

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents an alkyl group; R ₅ represents an alkyl group having 1 to 6 carbon atoms), and an ammonium salt structure By polymerizing a mixture containing a trialkoxysilane containing a radical polymerizable monomer, a polymer containing at least the trialkoxysilane as a monomer and a polymer of the radical polymerizable monomer It is characterized by producing a semi-IPN type composite.

  According to this, the above-described antifouling resin can be satisfactorily produced in a sol form. At this time, since the trialkoxysilane is compatible with most radical polymerizable monomers (that is, easily mixed with each other), an antifouling resin can be produced with a material selected from a wide range. Further, by obtaining a sol-like antifouling resin, the storage stability is improved, and the resin can be formed by a conventional simple coating method.

  Moreover, it is preferable that the manufacturing method of the antifouling resin of this invention contains the said trialkoxysilane in 1 to 100 weight% with respect to a mixture. As a result, a polymer containing trialkoxysilane having good biorepellency and antibacterial properties can be produced, and a polymer composed of a radical polymerizable monomer and a semi-IPN complex can be formed.

  In the method for producing an antifouling resin of the present invention, it is preferable that the radical polymerizable monomer is contained in the mixture in an amount of 1 wt% to 100 wt%. According to this, since a polymer comprising a radical polymerizable monomer is well complexed with a polymer containing trialkoxysilane to form a semi-IPN type complex, the antifouling resin is a good sol. This improves the storage stability and is easy to use.

  In the method for producing an antifouling resin of the present invention, it is preferable to add 2,2-azobis-isobutyronitrile to the above mixture. According to this, formation of a semi-IPN type complex of a polymer containing trialkoxysilane and a polymer composed of a radical polymerizable monomer can be promoted, and a semi-IPN type complex can be satisfactorily formed.

  Moreover, since the antifouling paint of the present invention contains the antifouling resin, it has antibacterial properties and biological repellent properties, is excellent in preservability, and is easy to use.

  As described above, the antifouling resin of the present invention includes at least a silicone resin obtained by polymerizing a trialkoxysilane having an ammonium salt structure as a monomer, represented by the general formula (1), and a radical polymerizable property. And a semi-IPN type composite containing the polymer.

  According to this, since the silicone resin has effective biorepellency and antibacterial properties, it is effective as an antibacterial material or an antifouling resin such as a resin that prevents adhesion of microorganisms and marine organisms in the ocean. In addition, since the silicone resin forms a radically polymerizable polymer and a semi-IPN type composite, it has excellent storage stability and can be used easily.

  Moreover, the manufacturing method of the antifouling resin of this invention polymerizes the mixture containing the trialkoxysilane containing an ammonium salt structure represented by the said General formula (1), and a radically polymerizable monomer. Thus, a semi-IPN complex of the trialkoxysilane polymer and the radical polymerizable monomer polymer is produced.

  According to this, since the trialkoxysilane and the radical polymerizable monomer are excellent in compatibility, an antifouling resin can be produced with a material selected from a wide range. Further, since the antifouling resin can be formed in a sol state, it is easy to store and use.

  The present invention is a paint having an effect of preventing microorganisms such as bacteria from adhering to the marine structure and further preventing organisms adhering to the marine structure as scaffolding (for example, animals such as barnacles, mussels, Aosa and diatoms). And an antifouling resin as a component thereof.

  As shown in FIG. 1, the inventors have used quaternary ammonium having an analog of choline known as an adhesion repellent active substance derived from a natural product, that is, octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride (OTAC). A semi-IPN type composite having a network invasion structure and a poly-methyl methacrylate entangled with each other, and having a biological repellent property and an antibacterial property, and does not solidify after polymerization. I found.

  According to this, since the antifouling resin has both antibacterial activity and adhesion repellent activity, it prevents the adhesion of marine organisms by preventing the adhesion of microorganisms, and also prevents the adhesion of marine organisms by the adhesion repellent activity. Long-term antifouling effect can be expected.

  Furthermore, since the resin does not solidify after polymerization, it can be stored for a long period of time in the form of a gel or a liquid obtained by diluting the gel, and if applied by an existing construction technique such as an applier spray, a sol- A film can be formed by a gel method and an antifouling effect can be easily imparted.

  The antifouling resin of the present invention is not limited to the above examples, and at least a silicone resin obtained by polymerizing a trialkoxysilane having an ammonium salt structure as a monomer represented by the general formula (1) above. And a semi-IPN complex containing a radical polymerizable polymer.

  As a method for producing the antifouling resin, a mixture containing a trialkoxysilane containing an ammonium salt structure represented by the general formula (1) and a radical polymerizable monomer may be polymerized.

  Since trialkoxysilane containing an ammonium salt structure has antibacterial properties and adhesion repellent properties, silicone resins also have antibacterial properties and biological repellent properties. The trialkoxysilane containing an ammonium salt structure is not particularly limited, but octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride (OTAC) is particularly preferable because of its high antibacterial activity and biological adhesion repellent activity. . By using the OTAC, the antifouling activity of the obtained antifouling resin is enhanced.

  Moreover, as a silicone resin, it is sufficient that at least a trialkoxysilane having an ammonium salt structure is included as a monomer, and even a polymer having only a trialkoxysilane having an ammonium salt structure as a monomer, Polymers using other compounds as monomers may also be used. In addition, tetraalkoxysilane is mentioned as another monomer, In this case, antifouling resin can be manufactured at low cost.

  Here, since the silicone resin of the present invention contains trialkoxysilane containing an ammonium salt structure as a monomer, a polymer containing trialkoxysilane containing an ammonium salt structure as a crosslinking agent is not included.

  A silicone resin using a trialkoxysilane containing an ammonium salt structure as a crosslinking agent (for example, a silicone resin in which a linear polysiloxane is crosslinked with the trialkoxysilane) increases the content of the trialkoxysilane more than a certain level. In contrast, the antifouling resin of the present invention can contain trialkoxysilane at a higher rate, and thus exhibits higher antibacterial and biological repellent properties. In addition, when trialkoxysilane is used as a crosslinking agent and a functional radical polymer that enhances the antifouling effect is added, the silicone resin material must be selected in consideration of compatibility with the radical polymerizable polymer. However, since the antifouling resin of the present invention has a high antifouling effect of the silicone resin, it is not always necessary to add a functional radical polymerizable polymer, and it is not necessary to select a material in consideration of compatibility.

  The trialkoxysilane containing an ammonium salt structure is preferably mixed within the range of a lower limit of 1% by weight and an upper limit of 100% by weight with respect to the entire mixture during resin production. If it is out of the above range, a good resin cannot be obtained. The lower limit is more preferably 30% by weight, and the upper limit is more preferably 60% by weight.

  In the method for producing an antifouling resin, it is desirable that the mixture further contains at least one radical polymerizable monomer.

  The radical polymerizable monomer is not particularly limited as long as it has radical polymerizability, and examples thereof include vinyl polymers and olefin polymers. Examples thereof include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, phthalic acid, and itaconic acid. In addition, half esters such as maleic acid ethyl ester, fumaric acid ethyl ester, itaconic acid ethyl ester, succinic acid mono (meth) acryloyloxyethyl ester, phthalic acid mono (meth) acryloyloxyethyl ester, or oleic acid, linoleic acid Synthetic unsaturated fatty acids such as ricinoleic acid and natural unsaturated fatty acids such as linseed oil and soybean oil may be used. Of these, alkyl methacrylate is preferable, and methyl methacrylate is particularly preferable. These radically polymerizable monomers may be used alone or in combination.

  The radical polymerizable monomer has at least a part of a functional radical polymerizable monomer having a functional side chain in order to impart a function to the resulting antifouling resin. It may be. By using such a functional radical polymerizable monomer, a function required for the antifouling resin to be obtained can be imparted.

  Examples of such a functional radical polymerizable monomer include N- (pn-octylphenyl) methacrylamide. The N- (pn-octylphenyl) methacrylamide is a monomer disclosed in Patent Document 2 and is known as a monomer having good aquatic organism repellent activity. By blending such N- (pn-octylphenyl) methacrylamide as a functional radical polymerizable monomer, the antifouling activity of the resulting antifouling resin is further enhanced.

  The N- (pn-octylphenyl) methacrylamide is a compound having an octylaniline group, which has been conventionally known as an antifouling agent, and such N- (pn-octylphenyl) methacrylamide is referred to as an antifouling agent. By blending and forming a semi-IPN type complex, higher antifouling activity can be obtained.

  However, when producing a semi-IPN type complex with such a functional radical polymerizable monomer, only limited materials can be used in consideration of compatibility as described above. For this reason, when the polymer containing trialkoxysilane containing an ammonium salt structure exhibits a sufficient antifouling effect, the functional radical polymerizable monomer may not be used.

  The radical polymerizable polymer is preferably mixed within the range of the lower limit of 1% by weight and the upper limit of 100% by weight with respect to the entire mixture during resin production. If it is out of the above range, a good resin cannot be obtained. The lower limit is more preferably 30% by weight, and the upper limit is more preferably 60% by weight.

  The ratio of the radical polymerizable monomer to the trialkoxysilane containing an ammonium salt structure is preferably in the range of a lower limit of 0.1 / 99.9 and an upper limit of 99.9 / 0.1 in terms of molar ratio. If it is out of the above range, a good semi-IPN type composite may not be formed. The lower limit is more preferably 1/99, and the upper limit is more preferably 99/1.

  The method for producing the antifouling resin used in the present invention is to polymerize a uniform mixture comprising the above-mentioned components. That is, when the reaction proceeds with each monomer component uniformly mixed, the trialkoxysilane resin and the radical polymerizable polymer are entangled with each other, and the antifouling property is a good semi-IPN type composite. A resin is formed. Uniform here means that each component does not cause phase separation and exists as a single phase. When the phase-separated mixture is polymerized as it is, a good semi-IPN type composite cannot be obtained, and therefore it is necessary to be uniform in the state of the mixture.

  In order to make the mixture uniform, the compatibility between the trialkoxysilane containing an ammonium salt structure and the radically polymerizable monomer is important. However, since trialkoxysilane containing an ammonium salt structure and a radical polymerizable monomer that is not a functional radical polymerizable monomer have relatively good compatibility in any combination, a wide range of materials is used. it can.

  In order to uniformly mix the components, the homogeneous mixture preferably contains a solvent as long as the formation of the semi-IPN complex is not hindered. Although it does not specifically limit as said solvent, The boiling point in a normal pressure is 150 degrees C or less, and the solvent which does not contain active hydrogen, such as a hydroxyl group and an amino group, is preferable. Specific examples include propanol, tetrahydrofuran, dichloroethane, acetonitrile, toluene and the like. The solvent is preferably blended within the range of the lower limit of 1% by weight and the upper limit of 99% by weight in the homogeneous mixture. When the above upper limit is exceeded, a dilute solution is obtained, so that entanglement between polymers is difficult to occur, and when it is less than the above lower limit, a good uniform mixture cannot be obtained, which is not preferable.

  The homogeneous mixture preferably contains a substance that undergoes polymerization with heat or ultraviolet light and induces a polymerization reaction of the radical polymerizable monomer. Such a substance is not particularly limited, and examples thereof include 2,2-azobis-isobutyronitrile, 2,2-azobiscyclohexylnitrile, dicumyl peroxide, benzoyl peroxide, and the like. The uniform mixture may have other components as necessary.

  Moreover, in this invention, since the compatibility of a mixing | blending component is favorable, what is necessary is just to perform a polymerization reaction at fixed temperature, stirring. Although it does not specifically limit as heating temperature, It is preferable to exist in the range of a minimum 60 degreeC and an upper limit 120 degreeC. The reaction time is preferably in the range of 1 minute to 48 hours in total.

  It can be confirmed by DSC (Differential Scanning Calorimeter) that the antifouling resin thus obtained has a semi-IPN type structure. That is, when a trialkoxysilane containing an ammonium salt structure is mechanically mixed with a radically polymerizable polymer, it cannot be mixed sufficiently to form a semi-IPN type composite. In the measurement, Tg and endothermic peak are merely superposition of homopolymers, and are not changed at all from the thermophysical properties of the homopolymer.

  On the other hand, the semi-IPN type composite prepared by the method for producing the semi-IPN type composite of the present invention differs from the homopolymer in the thermal behavior as measured by DSC, and particularly the Tg value changes. Therefore, it can be judged that it has a molecular structure that cannot be obtained by mechanical mixing.

  In addition, the obtained semi-IPN type composite preferably contains 60% by weight or more of trialkoxysilane containing an ammonium salt structure and a radical polymerizable polymer, and preferably contains 75% by weight or more.

  In the antifouling paint of the present invention, the antifouling resin is preferably blended within a range of a lower limit of 0.1% by weight and an upper limit of 99.9% by weight. If it is less than the above lower limit, sufficient antifouling properties cannot be exhibited, and if it exceeds the above upper limit, it becomes highly viscous and the coating workability is lowered.

  The antifouling paint of the present invention may contain other resins in addition to the antifouling resin. The other resin is not particularly limited. For example, polyester resin, chlorinated rubber, chlorinated polypropylene resin, styrene-butadiene resin, epoxy resin, polyamide resin, petroleum resin, wax, paraffin, rosin ester, Examples thereof include rosin resins. These may be used alone or in combination of two or more.

  The antifouling paint of the present invention may further contain conventional additives such as an antifouling agent, a plasticizer, a pigment, and a solvent as long as the performance of the paint is not impaired. The antifouling agent is not particularly limited, and a known one, for example, an inorganic compound, an organic compound containing a metal, an organic compound containing no metal, or the like may be used. Specifically, cuprous oxide, Manganese ethylene bisdithiocarbonate, zinc dimethylcarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,6-tetrachloro Isophthalonitrile, N, N-dimethyldichlorophenylurea, zinc ethylenebisdithiocarbamate, rhodan copper, 4,5-dichloro-2-n-octyl-3 (2H) isothiazolone, N- (fluorodichloromethylthio) sulfamide, 2 -Pyridinethiol-1-oxide zinc salt and copper salt, tetramethylthiuram disulfide, 2,4,6-trichlorophenylmaleimide, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 3- Iodo-2-propylbutylcarbamate, jodomethyl Ratorisuruhon, phenyl (bispyridyl) bismuth dichloride, 2- (4-thiazolyl) - benzimidazole, triphenylboron pyridine salt, stearylamine - triphenylboron, laurylamine - can be exemplified triphenyl boron, and the like. These antifouling agents may be used alone or in combination of two or more.

  Examples of the plasticizer include phthalate ester plasticizers such as dioctyl phthalate, dimethyl phthalate, and dicyclohexyl phthalate; aliphatic dibasic acid ester plasticizers such as isobutyl adipate and dibutyl sebacate; diethylene glycol dibenzoate, pentaerythritol Glycol ester plasticizers such as alkyl esters; Phosphate ester plasticizers such as tricylene phosphate and trichloroethyl phosphate; Epoxy plasticizers such as epoxy soybean oil and octyl epoxy stearate; Dioctyl tin laurate, Dibutyl tin laurate And organic tin plasticizers such as trioctyl trimellitic acid and triacetylene. These plasticizers may be used alone or in combination of two or more.

  Examples of the pigment include extender pigments such as precipitated barium, talc, clay, chalk, silica white, alumina white, bentonite; titanium oxide, zircon oxide, basic sulfate, tin oxide, carbon black, graphite, bengara, Mention may also be made of colored pigments such as chrome yellow, phthalocyanine green, phthalocyanine blue and quinacridone. These pigments may be used alone or in combination of two or more.

  Examples of the solvent include hydrocarbons such as toluene, xylene, ethylbenzene, cyclopentane, octane, heptane, cyclohexane, and white spirit; dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Ethers such as ethyl glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; esters such as butyl acetate, propyl acetate, benzyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethyl isobutyl ketone, methyl isobutyl Ketones such as ketones; n-butanol, propyl alcohol Mention may be made of the alcohol, and the like. These solvents may be used alone or in combination of two or more.

  Other additives include, for example, monobasic organic acids such as monobutyl phthalate and monooctyl succinate, camphor, castor oil, etc .; water binder, sagging agent; anti-coloring agent; anti-settling agent; antifoaming agent, etc. Can be mentioned.

  The antifouling paint is added to the antifouling resin, for example, by adding conventional additives such as the antifouling agent, plasticizer, coating film consumption regulator, pigment, solvent, ball mill, pebble mill, roll mill, sand grind. It can prepare by mixing using mixers, such as a mill. The antifouling paint can be applied to the surface of an object to be coated according to a conventional method, and then a dry coating film can be formed by removing the solvent by evaporation at room temperature or under heating.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims, and the embodiments can be obtained by appropriately combining technical means disclosed in different embodiments. The form is also included in the technical scope of the present invention.

  Hereinafter, the present invention will be described in more detail with reference to examples.

  The reagent uses octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride (hereinafter referred to as OTAC) as a trialkoxysilane containing an ammonium salt structure, and is a radically polymerizable monomer. Methyl methacrylate (hereinafter referred to as MMA) was used. As OTAC, a commercial product GELEST dissolved in methanol at a purity of 60% was used.

As shown in FIG. 2, OTAC (1124 μl), MMA (1068 μl), and 2-propanol (184 μl) were mixed to obtain a solution 1. Then, H ₂ O (109 μl), HCl (6 μl), 2-propanol (184 μl) and THF (2 ml) were mixed to obtain a solution 2. After mixing this solution 1 and solution 2, AIBN (0.0657 g) was added and stirred at room temperature for 30 minutes. Next, after cooling using a Dimroth, it stirred at 80 degreeC under nitrogen for 8 hours.

  After completion of the reaction, the solution increased in viscosity and changed to a viscous sol state (viscous solution). Then, when this viscous sol was applied to a substrate and dried, a film (sample) was formed through a wet gel state (after standing at room temperature for 30 minutes) and a dry gel state.

  Further, when the obtained sol was diluted with tetrahydrofuran, it could be stably stored in a diluted sol state for a long period of more than half a year. When this diluted sol was applied to the substrate with an applier, spray, brush, or the like, it quickly solidified and a resin thin film was formed on the substrate surface. This resin did not re-dissolve after contact with an organic solvent or water after solidification.

[Antimicrobial experiment using bacteria]
Regarding the IPN type complex of the sample obtained in the above-mentioned Examples and the OTAC homopolymer, the MMA polymer and the tetraethylorthosilicate (hereinafter TEOS) polymer as a comparative example, the marine bacterial strain No. 38 was obtained. The following antibacterial tests were performed.

First, a method for preparing a medium is shown. Filtered seawater was prepared by filtering natural seawater collected off the coast of Tokobo through a membrane filter system (polyvinylidene difluoride membrane, membrane pore diameter 0.45 mm). Polypepton; Commercial product (Nippon Pharmaceutical) 1.25 g, Yeast extract (Powder); Commercial product (Kanto Chemical) 1.25 g, Iron (II) sulfate heptahydrate (FeSO ₄ · 7H ₂ O); Commercial product (Wako Pure Chemical Industries, Ltd.) , Special grade) 0.10 g was added to 500 ml of filtered seawater and completely dissolved.

  After dissolution, the pH was adjusted to 7.21 with 0.05 mol / l Sodium hydroxide solution (0.05N-NaOH); (for Wako Pure Chemical Industries, volumetric analysis). The pH adjustment at this time is carried out using 100-7 pH STANDARD SOLUTION; commercial product (Horiba), 100-9 pH STANDARD SOLUTION; commercial product (Horiba) with pH METER F-22 (Horiba). It was.

  This prepared solution was dispensed into an Erlenmeyer flask, stoppered with aluminum foil, and then autoclaved. After sterilization, it was stored in a refrigerator (4 ° C.), which was used as a medium stock solution.

  The medium stock solution was filtered twice with No. 2 filter paper (Advantic) to remove precipitates generated by autoclaving. At this time, high-pressure steam sterilization was performed using AUTOCLAVE ES-215 (Tomy Industries, Ltd.) under sterilization conditions of 1.2 atmospheres × 121 ° C. × 20 minutes. 250 ml of this solution was placed in a 500 ml Erlenmeyer flask, Agar; 6.25 g of a commercial product (Wako Pure Chemical Industries, Ltd.) was added and the solution was stoppered with aluminum foil and then autoclaved. After sterilization, the medium was taken out while hot, dispensed 2.5 ml each into a sterilized petri dish in a clean bench, and radiated at room temperature. After the medium was completely solidified, the petri dish was inverted and stored in the refrigerator.

  Next, the subculture method of marine bacteria No. 38 will be described. Transplantation of marine bacteria No. 38 was all performed in a clean bench. First, the above-mentioned agar medium stored in the refrigerator and the stock of marine bacterium No. 38 were returned to room temperature, 1 platinum ear scraped from the passage stock, and the strain was streaked on the agar medium. The streaked culture medium was cultivated in a 25 ° C. incubator until sufficient fungi grew on the streaked portion (12 hours) and stored in the refrigerator.

  Then, the method of an antibacterial test is demonstrated. The liquid medium for antibacterial test was prepared as follows. The medium stock solution was filtered twice with No. 2 filter paper (Advantic) to remove precipitates generated by autoclaving. This solution was 200 ml in a 300 ml Erlenmeyer flask and 100 ml in a 200 ml Erlenmeyer flask, stoppered with aluminum foil, and then autoclaved as described above. After sterilization, the presence or absence of a precipitate was confirmed, and if there was no precipitate or a very small amount, it was stored in a refrigerator as it was. At this time, when the precipitation was large and turbid, it was prepared again from the medium stock solution.

  The polymer of Example or Comparative Example (7.8 mg) was dissolved or swollen in 0.1 ml of chloroform, cast into a sterilized centrifuge tube, dried at room temperature for 1 hour, and then vacuum dried for 12 hours. After drying, this was plugged with aluminum foil and then autoclaved. All subsequent operations were performed in a clean bench.

  To the sample prepared above, 2 ml of a liquid medium containing marine bacterial strain No. 38 was added and incubated at 37 ° C. for 12 hours. After incubation, 1 ml of this liquid medium was taken and transferred to another 4 ml of sterile liquid medium, and the antibacterial activity was examined from the turbidity (OD) of the medium. The turbidity of the medium was measured using a digital colorimeter (PHOTO METER mini photo 518, Taitec).

  As a result, after 12 hours, in the medium containing the sample of the comparative example (POTAC) or the sample of Example 1, the marine bacterial strain No. The growth of 38 (bacteria) was suppressed, and the medium was transparent. On the other hand, in the medium containing the IPN type complex of MMA polymer (PMMA) and TEOS polymer, marine bacterial strain No. 38 grew and became cloudy. Therefore, it was found that the semi-IPN type complex of the present invention exhibits antibacterial activity.

[Measurement of biological repellent activity using mussels]
Regarding the sample containing 75% by weight of OTAC in the semi-IPN complex obtained in Example 1, the marine organism adhesion repellent activity is described in Patent Document 3 “Substance to repel marine deposits (above) (Ina)”. Evaluation was made based on the “flat plate foot thread measurement method (test plate method)”. Further, as another example, a solution in which the amount of OTAC and TEOS in the solution 1 was changed at the time of production was prepared so that the amount of OTAC contained in the semi-IPN composite was 25 or 50% by weight. That is, the mixture prepared by mixing PMMA: TEOS: OTAC = 2: 1: 1 in the mixed solution is an example in which the amount of OTAC contained in the semi-IPN composite is 25% by weight. The case where PMMA: TEOS: OTAC = 4: 1: 3 is an example in which the amount of OTAC is 50% by weight. In addition, OTAC homopolymers (with an OTAC content of 100% by weight) and TBTO (tributyltin oxide) as comparative examples were also evaluated. In addition, 4 mussels per sample were used as subjects, and the determination was performed as follows.

First, let A be the number of foot threads outside the sample zone of one mussel, and B be the total number of foot threads. And
1) When B ≧ 7, if A / B ≧ 2/3, the point of the mussel is set to +2. If A / B <2/3, -2.
2) When 2 ≦ B ≦ 6, the point of the mussel is obtained from Table 1.

  Next, a total point (Tp) for four mussels is obtained.

  In addition, when the total number of foot threads of one individual was 0 or 1, the average value of the remaining three individuals was used as the point of the individual group. When the total number of foot threads of two or more individuals was 0 or 1, a retest was performed and the average value of the two tests was given.

  From the total points measured as described above, the relative values of the biological repellency of other examples when the biological repellency of TBTO was set to 100 were obtained. The results are shown in FIG. According to this, when the OTAC in the semi-IPN is 25% by weight or 50% by weight, the biological repellent activity is 30 to 40, whereas when the OTAC in the semi-IPN is 75% by weight, a value close to 100 is shown. It was. From this, it can be seen that when the semi-IPN complex OTAC has a value greater than 50% by weight, the biological repellent activity significantly increases. It can also be seen that when OTAC is 75% by weight or more, there is a very strong biological repellent activity.

  Further, in the comparative example OTAC homopolymer (100% OTAC in semi-IPN), the value was close to 100%.

  As a result, the antifouling resin using OTAC and MMA in this example had sufficient antibacterial properties and biorepellency comparable to OTAC homopolymer and TBTO. Therefore, it was found that the resin of this example had both antibacterial properties and biofouling repellency.

It is drawing which shows the chemical formula of the octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride used for manufacture of the antifouling resin which concerns on a present Example. It is drawing which shows the manufacturing method of antifouling resin which concerns on a present Example. It is drawing which shows the measurement result of the adhesion repellent activity of the antifouling resin which concerns on a present Example.

Claims (11)

At least the general formula (1);

(Wherein, R ₁ , R ₂ , R ₃ and R ₄ each independently represents an alkyl group. R ₅ represents an alkyl group having 1 to 18 carbon atoms) A silicone resin obtained by polymerizing a trialkoxysilane having a monomer as a monomer;
An antifouling resin comprising a semi-IPN type composite containing a radical polymerizable polymer.   The antifouling resin according to claim 1, wherein the trialkoxysilane is octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride.   The antifouling resin according to claim 1 or 2, wherein the radical polymerizable polymer is polymethyl methacrylate.   4. The antifouling resin according to claim 1, wherein the trialkoxysilane is contained in the semi-IPN type composite in an amount of 60% by weight or more. 5.   The antifouling resin according to any one of claims 1 to 4, wherein the silicone resin comprises trialkoxysilane.   The antifouling resin according to any one of claims 1 to 4, wherein the silicone resin comprises the trialkoxysilane and the tetraalkoxysilane. General formula (1);

(Wherein, R ₁ , R ₂ , R ₃ and R ₄ each independently represents an alkyl group. R ₅ represents an alkyl group having 1 to 18 carbon atoms) Trialkoxysilane containing
By polymerizing a mixture containing a radical polymerizable monomer,
A method for producing an antifouling resin, comprising producing a semi-IPN type complex of a polymer having at least the trialkoxysilane as a monomer and a polymer of the radical polymerizable monomer.   The method for producing an antifouling resin according to claim 1 or 2, wherein the trialkoxysilane is contained in an amount of 1 wt% to 100 wt% with respect to the mixture.   The radical polymerizable monomer is contained in the mixture in an amount of 1 wt% to 100 wt%.   The method for producing an antifouling resin according to any one of claims 7 to 9, wherein 2,2-azobis-isobutyronitrile is added to the mixture.   An antifouling paint comprising the antifouling resin according to any one of claims 1 to 6.

Images