JP4386190B2 - Antifouling condensation-curing organopolysiloxane composition and underwater structure - Google Patents

Description

  The present invention relates to a room temperature curable organopolysiloxane composition suitable as a coating material, and in particular, a ship, a port facility, a buoy, a pipeline, a bridge, a submarine base, a submarine oil field drilling facility, a power plant conduit pipe, and a culture net Room temperature curing type that can be applied to stationary nets (hereinafter collectively referred to as “underwater structures”) to provide an antifouling coating suitable for preventing the attachment and growth of aquatic organisms on these surfaces The present invention relates to an organopolysiloxane composition and an underwater structure coated with a cured product of the composition.

  Conventionally, various room temperature curable silicone rubber compositions that give rubber-like elastic bodies at room temperature are known. A cured rubber obtained from a room temperature curable silicone rubber composition (hereinafter referred to as “RTV”) has superior weather resistance, durability, heat resistance, cold resistance, etc. compared to other organic rubbers. It is used in various fields, and particularly in the field of architecture, it is frequently used for bonding between glasses, bonding between metal and glass, sealing concrete joints, and the like. In recent years, it has been widely used as a coating material for buildings, plants, water pipe inner surfaces, water pipe outer surfaces, and the like.

  However, the organopolysiloxane, which is the main component of this RTV, has the property of being easily charged and easily adsorbs dust in the atmosphere. Therefore, the surface of the cured sealing material or coating material becomes very dirty over time, and the appearance is beautiful. There was a problem of damaging. As a method for solving this problem, for example, a method in which a surfactant having a polyoxyethylene group, a sorbitan residue, a disaccharide residue or the like is added to and blended with RTV has been proposed (Patent Documents 1 and 2: JP-A No. 2005-151405). (See Japanese Laid-Open Patent Publication No. 56-76452 and Japanese Laid-Open Patent Publication No. 56-76453). However, in order to obtain a sufficiently satisfactory effect by the above-described method, it is necessary to add a large amount of a surfactant. Therefore, the adhesiveness is an important function as an RTV sealing material or coating material. Has the disadvantage of causing

  In addition, when an underwater structure is installed or put into service, barnacles, squirts, cell plastics, mussels, crows, chrysanthemum, aonori, aosa that live in the water of the sea, rivers, etc. from the splashed part to the surface of the submerged part. Aquatic organisms such as these attach and grow, causing various damage. For example, when organisms adhere to the hull, the frictional resistance with water increases, the navigation speed decreases, and fuel consumption increases to maintain a constant speed, which is economically disadvantageous. Moreover, if a living thing adheres to the structure fixed to the water or the water surface of a port facility etc., it will become difficult to fully exhibit each function which these have, and a base material may be eroded. Furthermore, if organisms adhere to aquaculture nets, stationary nets, etc., the nets may be blocked and fish may die.

  As measures to prevent the attachment and growth of aquatic organisms to underwater structures, antifouling paints containing toxic antifouling agents such as organotin compounds and cuprous oxide were applied to the structures. Although adherence and growth of living organisms were almost prevented, a toxic antifouling agent was used, which is undesirable for environmental safety and hygiene during the manufacture and painting of paints. In the long term, there is a risk of contaminating the water area, so its use is legally prohibited.

  On the other hand, as a paint which has an effect of preventing adhesion and growth of aquatic organisms and does not contain a toxic antifouling agent, liquid paraffin or petrolatum is added to RTV as an antifouling property by lowering the surface tension of the coating film. A non-toxic antifouling paint blended has been proposed (see Patent Documents 3 and 4: Japanese Patent Laid-Open Nos. 58-13673 and 62-84166). In addition, volumetric shrinkage associated with the curing of the reaction-curable silicone resin causes the non-reactive and non-reactive polar group-containing silicone resin to bleed out onto the surface, preventing the combination with the low surface tension of the reaction-curable silicone resin. Non-toxic antifouling paint compositions exhibiting soiling properties (see Patent Documents 5 and 6: Japanese Patent Nos. 2503986 and 295375) have also been proposed. However, the non-toxic antifouling coating composition is a polyoxyethylene in which ethylene oxide, propylene oxide, etc. are added to Si atoms via a C—C bond in a poorly compatible and non-reactive polar group-containing silicone resin. Since the silicone resin having a group or the silicone resin in which an alkoxy group is introduced into the molecular terminal through an ethylene oxide or propylene oxide group in Si atom is oil-bleeded, there is a problem in environmental safety and health.

  Japanese Patent Application Laid-Open No. 2003-119388 (Patent Document 7) discloses that a base polymer is a diorganopolysiloxane in which 2 mol% or more of all substituents bonded to silicon atoms are monovalent hydrocarbon groups having 2 or more carbon atoms. The non-staining silicone rubber composition was proposed, but the antifouling property in water was not satisfactory.

Japanese Patent Laid-Open No. 56-76452 JP 56-76453 A JP 58-13673 A JP-A-62-84166 Japanese Patent No. 2503986 Japanese Patent No. 2952375 JP 2003-119388 A

  The present invention has been made in view of the above circumstances, and is particularly suitable for preventing adhesion and growth of aquatic organisms on the surface of an underwater structure, which is coated on the underwater structure, and has a sustained effect. The present invention provides an antifouling condensation-curing organopolysiloxane composition that provides a good and antifouling coating that solves environmental health and safety problems and cures by a condensation reaction, and an underwater structure coated with this composition. Objective.

In order to achieve the above-mentioned object, the present inventors have intensively studied the antifouling effect by the oil bleed used in the prior art in the antifouling RTV that cures by condensation reaction. , A silicone oil having no phenyl group and no reactive group, particularly dimethylpolysiloxane oil and / or diethylpolysiloxane oil, and the structure of the diorganopolysiloxane as the base polymer is represented by the following general formula (1) and / or or (2) results of the specified shall indicated by found that excellent antifouling property can be obtained.

  That is, in the present invention, the condensation-curing organopolysiloxane composition having antifouling properties with the environmental safety and hygiene as the top has been intensively studied, and the oxyalkylene modified as a bleed oil component that has been conventionally used. Di, having a monovalent substituted or unsubstituted hydrocarbon group that does not have a reactivity bonded to a silicon atom without using components such as silicone, methylphenyl silicone, and dimethyldiphenyl silicone, which have not yet obtained environmental safety data. We examined the use of silicone oils with sufficient environmental safety data such as organopolysiloxane.

  Here, in the conventional antifouling condensation curable organopolysiloxane composition or silicone rubber composition, the substituent bonded to the silicon atom of the base polymer is described as a substituted or unsubstituted monovalent hydrocarbon group in patent documents and the like. Although there are many examples, methyl groups are usually used, and there are almost no examples using vinyl groups in practice.

  However, a diorganopolysiloxane that does not contain a phenyl group and has an alkenyl group such as a vinyl group as a substituent bonded to a silicon atom is selected. This bleed oil can prevent the attachment and growth of aquatic organisms on the surface of underwater structures, has a long-lasting effect, and provides an antifouling coating that solves environmental health and safety problems. It has been found that a functional organopolysiloxane composition can be obtained, and the present invention has been made.

（式中、Ｒは置換又は非置換の一価炭化水素基であるが、フェニル基は含まない。また、Ｒの２モル％以上が置換又は非置換のアルケニル基である。Ｘは酸素原子又は炭素数１〜８の二価炭化水素基であり、ｎはこのジオルガノポリシロキサンの２５℃における粘度を１００〜１，０００，０００ｍｍ ² ／ｓとする数である。）

（式中、Ｙは加水分解性基であり、ａは２又は３であり、Ｒは置換又は非置換の一価炭化水素基であるが、フェニル基は含まない。また、Ｒの２モル％以上が置換又は非置換のアルケニル基である。Ｘは酸素原子又は炭素数１〜８の二価炭化水素基であり、ｎはこのジオルガノポリシロキサンの２５℃における粘度を１００〜１，０００，０００ｍｍ ² ／ｓとする数である。）
で表されるジオルガノポリシロキサン、
（Ｂ）加水分解性基を１分子中に２個以上有するシラン及び／又はその部分加水分解縮合物、及び
（Ｃ）フェニル基及び珪素原子に結合した反応性基を有しないシリコーンオイル
を配合してなる防汚性縮合硬化型オルガノポリシロキサン組成物、及びこの組成物の硬化物でコーティングされた水中構造物を提供する。 Therefore, the present invention
(A) As a base polymer, the following general formula (1) and / or (2)

(In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group, but does not include a phenyl group. Further, 2 mol% or more of R is a substituted or unsubstituted alkenyl group. X is an oxygen atom or C is a divalent hydrocarbon group having 1 to 8 carbon atoms, and n is a number that makes the viscosity of this diorganopolysiloxane at 25 ° C. 100 to 1,000,000 mm ² / s.)

(In the formula, Y is a hydrolyzable group, a is 2 or 3, R is a substituted or unsubstituted monovalent hydrocarbon group, but does not contain a phenyl group. Also, 2 mol% of R The above is a substituted or unsubstituted alkenyl group, X is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, and n is a viscosity of the diorganopolysiloxane at 25 ° C. of 100 to 1,000,000. 000 mm ² / s.)
Diorganopolysiloxane represented by
(B) A silane having two or more hydrolyzable groups in one molecule and / or a partially hydrolyzed condensate thereof, and (C) a silicone oil having no phenyl group and no reactive group bonded to a silicon atom. An antifouling condensation curable organopolysiloxane composition and an underwater structure coated with a cured product of the composition are provided.

  The coating film obtained from the antifouling condensation curable organopolysiloxane composition of the present invention is non-toxic, has no environmental problems, and prevents attachment and growth of aquatic organisms over a long period of time, It exhibits excellent antifouling properties.

The antifouling condensation curable organopolysiloxane composition of the present invention comprises the following components (A) to (C).
(A) as the base polymer, diorganopolysiloxane Ru represented by the following general formula (1) and / or (2).
(B) A silane having two or more hydrolyzable groups in one molecule and / or a partial hydrolysis condensate thereof.
(C) A silicone oil having no reactive group bonded to a phenyl group and a silicon atom.

[(A) component]
The diorganopolysiloxane which is the component (A) is the main component (base polymer) of the antifouling condensation curable organopolysiloxane composition of the present invention, and is a hydroxyl group or water bonded to at least two silicon atoms in the molecule. It has a decomposable group, does not contain a phenyl group, and 2 mol% or more of all substituents bonded to the silicon atom have an alkenyl group. As such a diorganopolysiloxane, specifically, a diorganopolysiloxane having a molecular chain terminal represented by the following general formula (1) or (2) blocked with a hydroxyl group or a hydrolyzable group is used.

（式中、Ｘは酸素原子又は炭素数１〜８の二価炭化水素基であり、Ｙは加水分解性基であり、ａは２又は３であり、Ｒは置換又は非置換の一価炭化水素基であるが、フェニル基を含有しない。また、Ｒの２モル％以上がアルケニル基である。ｎはこのジオルガノポリシロキサンの２５℃における粘度を１００〜１，０００，０００ｍｍ²／ｓとする数である。）

(Wherein X is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, Y is a hydrolyzable group, a is 2 or 3, and R is a substituted or unsubstituted monovalent carbonization. Although it is a hydrogen group, it does not contain a phenyl group, more than 2 mol% of R is an alkenyl group, and n is a viscosity of this diorganopolysiloxane at 25 ° C. of 100 to 1,000,000 mm ² / s. Number to do.)

  Here, R other than the alkenyl group does not contain a phenyl group and is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylbutyl group or an octyl group, a cycloalkyl group such as a cyclohexyl group or a cyclopentyl group. A chloromethyl group, a trifluoropropyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, etc. in which some or all of the hydrogen atoms bonded to the carbon atom of these groups or groups are substituted with halogen atoms, cyano groups, etc. The same or different unsubstituted or substituted selected from 1 is preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms, and preferably a methyl group.

Further, it is necessary that 2 mol% or more, preferably 2.5 mol% or more of R is an alkenyl group. The upper limit is not particularly limited and is 100 mol% or less, but is preferably 50 mol% or less from the viewpoint of ease of production.
Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a heptenyl group, and a hexenyl group, and a vinyl group is particularly preferable. Two or more different types may be used.

X is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, the divalent hydrocarbon group, - (CH _{2) m} - those (m represents 1-8) represented by preferable. Among these, an oxygen atom and —CH ₂ CH ₂ — are preferable.

  Y is a hydrolyzable group other than a hydroxyl group at the molecular chain end of the diorganopolysiloxane, for example, an alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group; a methoxyethoxy group, an ethoxyethoxy group, a methoxypropoxy group, or the like An alkoxy group such as an acetoxy group, an octanoyloxy group and a benzoyloxy group; an alkenyloxy group such as a vinyloxy group, an isopropenyloxy group and a 1-ethyl-2-methylvinyloxy group; a dimethyl ketoxime group; Ketoxime groups such as methyl ethyl ketoxime group and diethyl ketoxime group; Amino groups such as dimethylamino group, diethylamino group, butylamino group and cyclohexylamino group; Aminoxy groups such as dimethylaminoxy group and diethylaminoxy group; N-methylacetoa De group, N- ethyl acetamide group, and amide groups such as N- methylbenzamide group. Among these, an alkoxy group is preferable.

The diorganopolysiloxane of component (A), is preferably 100~1,000,000mm ² / s viscosity at 25 ° C., more preferably 300~500,000mm ² / s, particularly preferably from 500 to 100, 000 mm ² / s, especially 1,000 to 50,000 mm ² / s. If the viscosity of the diorganopolysiloxane is less than 100 mm ² / s (25 ° C.), it may be difficult to obtain a coating film having excellent physical and mechanical strength. If it exceeds 000 mm ² / s (25 ° C.), the viscosity of the composition becomes too high, and workability during use may be deteriorated.

Therefore, n in the formulas (1) and (2) is a number that makes the viscosity such a viscosity value.
Here, this viscosity is a value measured by a rotational viscometer.
Such a diorganopolysiloxane can be produced by a known method such as obtaining a cyclic siloxane or linear oligomer, which is a monomer of various organopolysiloxanes, by an equilibrium reaction with an acid or base catalyst.
When a branched structure is introduced into the diorganopolysiloxane, a silane or siloxane containing SiO _3/2 units and / or SiO _4/2 units is added at a level at which the diorganopolysiloxane does not gel during the equilibration polymerization. It is common practice to do this.

  Specific examples of the (A) component diorganopolysiloxane include the following.

（式中、ｎ、Ｒ、Ｙは上記と同様であり、ｍ’は０又は１である。）

(In the formula, n, R and Y are the same as above, and m ′ is 0 or 1.)

  The diorganopolysiloxane (A) can be used alone or in combination of two or more.

[Component (B)]
The silane having two or more hydrolyzable groups in one molecule and / or its partially hydrolyzed condensate as component (B) of the present invention is an essential component for curing the composition of the present invention. It is necessary to have at least two hydrolyzable groups bonded to a silicon atom in one molecule. As such an organosilicon compound, a silane represented by the following general formula (3) or a partially hydrolyzed condensate thereof can be exemplified.

R ¹ _b SiZ _4-b (3)
(In the formula, R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, Z is independently a hydrolyzable group, and b is an integer of 0 to 2.)

  Examples of the hydrolyzable group (Z) include those exemplified as the hydrolyzable group (Y) other than the hydroxyl group at the molecular chain end of the organopolysiloxane of the component (A). Group, ketoxime group and isopropenoxy group are preferred.

  The silane or partial hydrolysis condensate thereof, which is the component (B), is not particularly limited except that it must have at least two hydrolyzable groups as described above in its molecule. It is preferable to have 3 or more, and a group other than a hydrolyzable group may be bonded to the silicon atom, and the molecular structure may be either a silane or siloxane structure. In particular, those having a siloxane structure may be linear, branched or cyclic.

The group (R ¹ ) other than the hydrolyzable group is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, or pentyl. Group, alkyl group such as hexyl group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; aryl group such as phenyl group and tolyl group; aralkyl group such as benzyl group and 2-phenylethyl group; vinyl group, allyl group, butenyl Groups, alkenyl groups such as a pentenyl group and a hexenyl group; halogenated alkyl groups such as a 3,3,3-trifluoropropyl group and a 3-chloropropyl group. Among these, a methyl group, an ethyl group, a phenyl group, and a vinyl group are preferable.

  Specific examples of the organosilicon compound as the component (B) of the present invention include, for example, ethyl silicate, propyl silicate, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltris (methoxyethoxy). ) Silane, vinyltris (methoxyethoxy) silane, methyltripropenoxysilane, methyltriacetoxysilane, vinyltriacetoxysilane, methyltri (methylethylketoxime) silane, vinyltri (methylethylketoxime) silane, phenyltri (methylethylketoxime) silane, propyltri (Methylethylketoxime) silane, tetra (methylethylketoxime) silane, 3,3,3-trifluoropropyltri (methylethylketoxime) silane, 3- Rolopropyltri (methylethylketoxime) silane, methyltri (dimethylketoxime) silane, methyltri (diethylketoxime) silane, methyltri (methylisopropylketoxime) silane, tri (cyclohexanoxime) silane, etc., and their partial hydrolysis condensation Things. These can be used singly or in combination of two or more.

  (B) It is preferable that the compounding quantity of a component is 0.5-30 mass parts with respect to 100 mass parts of said (A) component, More preferably, it is 1-20 mass parts. If the blending amount is less than 0.5 parts by mass, crosslinking may be insufficient. Conversely, if it exceeds 30 parts by mass, the cured product may be too hard, which is economically disadvantageous. Sometimes.

[Component (C)]
It is known that the silicone oil that does not have a phenyl group and a reactive group bonded to a silicon atom, which is the component (C) of the present invention, can be used as a plasticizer in a normal room temperature curable composition. In the invention, it is used as a bleed oil, and is not particularly limited as long as it is a silicone oil that does not react with the component (A), but those represented by the following general formula (4) are preferably used. It is done.
Here, the reactivity means a condensation reaction with the hydroxyl group and hydrolyzable group of the component (A), and examples of the reactive group include a hydroxyl group and a hydrolyzable group.

（式中、Ｒ²はメチル基及び／又はエチル基であり、メチル基であることが好ましい。Ｘは酸素原子又は炭素数１〜８の二価炭化水素基であり、上述したＸと同様のものを例示することができる。ｐはこのジオルガノポリシロキサンの２５℃における粘度を１０〜１，０００，０００ｍｍ²／ｓとする数である。）

(In the formula, R ² is a methyl group and / or an ethyl group, and is preferably a methyl group. X is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, and is the same as X described above. (P is a number that makes the viscosity of this diorganopolysiloxane at 25 ° C. 10 to 1,000,000 mm ² / s.)

The diorganopolysiloxane of component (C) preferably has a viscosity at 25 ° C. The 10~1,000,000mm ² / s, more preferably 20~100,000mm ² / s, particularly preferably 50 to 50, 000mm ² / s, in particular 100~10,000mm ² / s. When the viscosity is less than 10 mm ² / s (25 ° C.), the oil bleed speed may be too high and the antifouling property may be inferior, and conversely, 1,000,000 mm ² / s ( If it exceeds 25 ° C., the viscosity of the composition becomes too high, the workability during use may be deteriorated, and the antifouling property may be deteriorated.

The viscosities of the component (A) and the component (C) are as described above, and the viscosity ratio at 25 ° C. is preferably (C) component / (A) component = 0.02-10, particularly 0. 0.05 to 8 is preferable. If this viscosity ratio is too large, the component (C) will hardly oil bleed, and the antifouling property may deteriorate immediately after immersion. If it is too small, the initial antifouling property will be good. There is a risk that the antifouling property is inferior in sustainability.
Among this, (A) the viscosity of the component at 1,000~20,000mm ² / s, particularly preferably a combination, the viscosity of component (C) is a 100~10,000mm ² / s.

  This component (C) has a very excellent surface activity. Therefore, it functions to prevent the adhesion of aquatic organisms to the silicone cured rubber film. That is, it is considered that the component blooming on the surface functions as a surfactant and contributes to the prevention of antifouling and antifouling action of aquatic organisms.

  The amount of component (C) is preferably 1 to 100 parts by weight, more preferably 3 to 70 parts by weight, and particularly preferably 5 to 50 parts by weight with respect to 100 parts by weight of component (A). It is. If the blending amount is less than 1 part by mass, the added effect may not be exhibited. Conversely, if the amount is more than 100 parts by mass, the cured film may become opaque or soften beyond the limit.

[Other ingredients]
A catalyst for further promoting curing may be added to the composition of the present invention. As such a curing catalyst, various ones used in condensation-curable room temperature curable compositions can be used. Specific examples include lead-2-ethyl octoate, dibutyltin dioctoate, dibutyl. Tin acetate, dibutyltin dilaurate, butyltin-2-ethylhexoate, iron-2-ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, zinc-2-ethylhexene Metal salts of organic carboxylic acids such as xoate, stannous caprylate, tin naphthenate, tin oleate, tin butanoate, titanium naphthenate, zinc naphthenate, cobalt naphthenate, zinc stearate; tetrabutyl titanate, tetra -2-ethylhexyl titanate, triethanolamine titanate, tetra (isopropenyloxy) titanate Organo-titanic acid esters such as organosiloxytitanium, β-carbonyltitanium and other organotitanium compounds; alkoxyaluminum compounds, 3-aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine and other aminoalkyl group-substituted alkoxy Silanes; amine compounds such as hexylamine and dodecylamine phosphate and salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate and lithium odorate; dimethylhydroxylamine Dialkylhydroxylamine such as diethylhydroxylamine;

等で表されるグアニジン化合物及びグアニジル基含有シラン若しくはシロキサン等を挙げることができる。これらは単独でも２種以上を組み合わせても使用することができる。

Guanidine compounds represented by the above and the like, and guanidyl group-containing silanes or siloxanes. These can be used alone or in combination of two or more.

  When the curing catalyst is used, the amount used is not particularly limited and may be an effective amount as a catalyst, but is usually preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the component (A). In particular, the content is preferably 0.1 to 10 parts by mass. When using this catalyst, if the content of the catalyst is less than the lower limit of the above range, the curability of the resulting composition may be insufficient depending on the type of the crosslinking agent, When the upper limit is exceeded, the storage stability of the resulting composition may decrease.

In the composition of the present invention, a filler may be used for the purpose of reinforcing or increasing the amount. Examples of such a filler include hydrophilic silica such as fumed silica and precipitated silica, silica, quartz, diatomaceous earth, and titanium oxide whose surface is hydrophobized with hexamethyldisilazane or cyclic dimethylsiloxane. , Aluminum oxide, Lead oxide, Iron oxide, Carbon black, Bentonite, Graphite, Calcium carbonate, Calcium silicate, Silica zeolite, Mica, Clay, Glass beads, Glass microballoon, Shirasu balloon, Glass fiber, Polyvinyl chloride beads, Polystyrene beads And acrylic beads. Among these, calcium carbonate, calcium silicate, silica zeolites, and BET specific surface area of 10 m ² / g or more, hydrophilic silica is preferable in particular 50 to 400 m ² / g.

  The blending amount of the filler may be selected depending on the purpose and the kind of the filler, but is usually 3 to 500 parts by weight, particularly 5 to 100 parts by weight with respect to 100 parts by weight of the diorganopolysiloxane component of the base polymer. Preferably there is.

  In the production of the composition of the present invention, the base polymer diorganopolysiloxane and the filler are preliminarily heat-treated at a temperature of 100 ° C. or higher, particularly 120 to 180 ° C., and then the components (C) and (B ) Component is preferred. The component (B) may be blended simultaneously with the component (C) or finally.

  The composition used in the present invention includes a plasticizer, a colorant such as a pigment, a flame retardant, a thixotropic agent, a fungicide / antibacterial agent, an amino group, an epoxy group, and a thiol group as necessary. A predetermined amount of an adhesion improver such as a so-called carbon functional silane (for example, γ-glycidoxypropyltrimethoxysilane or aminopropyltriethoxysilane) or the like is appropriately added within a range not impairing the object of the present invention. There is no problem to mix them.

  Examples of the underwater structure to which the present invention is applied include ships, harbor facilities, buoys, pipelines, bridges, submarine bases, subsea oil field drilling equipment, powerhouse conduit pipes, aquaculture nets, stationary nets, and the like. it can. In this case, the coating film thickness of the composition of the present invention is preferably 25 to 750 μm, particularly preferably 50 to 400 μm. In addition, what is necessary is just to apply | coat and harden the composition of this invention at room temperature (normal temperature).

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, all "parts" in each example indicate "parts by mass", and the viscosity indicates a value measured at 25 ° C. by a rotational viscometer.

[Synthesis Example 1]
Production of polymer A 2,5,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane 2, 752 g, distilled water 5.0 g, and potassium hydroxide 0.08 g were charged and reacted at 150 ° C. for 5 hours. After the reaction, the mixture was cooled to 80 ° C., 4.0 g of ethylene chlorohydrin was added, and further reacted at 80 ° C. for 3 hours, and then the low volatile matter was distilled off by heating under reduced pressure to obtain a viscosity of 5,000 mm ² / s, 2,400 g of a colorless transparent liquid having a nonvolatile content of 96.8% (both end-terminated hydroxyl-blocked polymethylvinylsiloxane, ratio of substituents having 2 or more carbon atoms to all substituents bonded to silicon atoms: 50 mol%) was obtained.

[Synthesis Example 2]
Production of polymer B 2,4,6,8-tetravinyl- 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane in 2,752 g in Synthesis Example 1 A viscosity of 4,700 mm ² / s and a non-volatile content of 96. except that 1,376 g of 2,4,6,8-tetramethylcyclotetrasiloxane and 1,184 g of octamethylcyclotetrasiloxane were used. 2,300 g of an 8% colorless transparent liquid (both end hydroxyl-blocked polymethylvinylsiloxane, ratio of substituents having 2 or more carbon atoms to all substituents bonded to silicon atoms: 25 mol%) was obtained.

[Synthesis Example 3]
Production of polymer C A colorless transparent liquid having a viscosity of 1,500 mm ² / s and a non-volatile content of 97.6% (both end-terminated hydroxyl-blocked poly) in the same manner as in Synthesis Example 1 except that 6.4 g of distilled water was used in Synthesis Example 1. 2,150 g of methyl vinyl siloxane and the ratio of substituents having 2 or more carbon atoms to all substituents bonded to silicon atoms (50 mol%) were obtained.

[Synthesis Example 4]
Production of polymer D Instead of 2,752, g of 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane in Synthesis Example 1, 2,4,6,8-tetravinyl- Viscosity: 4,600 mm ² / s, nonvolatile content: 98.7%, except that 275 g of 2,4,6,8-tetramethylcyclotetrasiloxane and 2,131 g of octamethylcyclotetrasiloxane were used 2,200 g of a colorless transparent liquid (both ends hydroxyl-blocked polymethylvinylsiloxane, ratio of substituents having 2 or more carbon atoms to all substituents bonded to silicon atoms: 5 mol%) was obtained.

[Synthesis Example 5]
Production of Polymer E 2,368 g of octamethylcyclotetrasiloxane was used instead of 2,752 g of 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane in Synthesis Example 1. Except for the above, in the same manner as in Synthesis Example 1, a colorless transparent liquid having a viscosity of 4,500 mm ² / s and a non-volatile content of 96.3% (both end-terminated hydroxyl-blocked polymethylvinylsiloxane, 2 carbon atoms relative to all substituents bonded to silicon atoms) 2,300 g of the above substituent ratio: 0 mol%) was obtained.

[Synthesis Example 6]
Production of polymer F 1,000 g of polymer A and 152 g of tetramethoxysilane were charged in a three-necked flask having an internal volume of 2 liters equipped with a thermometer, a stirrer and a condenser, and reacted at 120 ° C. for 24 hours. After the reaction, methanol and excess tetramethoxysilane are distilled off by heating under reduced pressure to obtain a colorless transparent liquid having a viscosity of 5,200 mm ² / s and a non-volatile content of 96.9% (trimethyl group-blocked polymethylvinylsiloxane, silicon atoms at both ends) 975 g of a ratio of the substituent having 2 or more carbon atoms to the total substituents bonded to was 50 mol%).

[Synthesis Example 7]
Production of polymer G A colorless transparent liquid having a viscosity of 4,700 mm ² / s and a non-volatile content of 98.2% (both ends) except that polymer E was used instead of polymer A of synthesis example 6 950 g of trimethoxy group-blocked polymethylvinylsiloxane and the ratio of substituents having 2 or more carbon atoms to all substituents bonded to silicon atoms were obtained.

[Example 1]
70 parts of polymer A and 15 parts of fumed silica having a specific surface area of 200 m ² / g were uniformly mixed and heated under reduced pressure at 150 ° C. for 2 hours. To this, 12 parts of vinyltris (methylethylketoxime) silane and 1 part of γ-aminopropyltriethoxysilane were mixed under reduced pressure until uniform. Further, a composition was prepared by mixing 30 parts of α, ω-trimethylsiloxy-dimethyl-polysiloxane having a viscosity of 100 mm ² / s until uniform under reduced pressure.

[Examples 2 to 4]
A composition was prepared in the same manner as in Example 1 except that the polymer A in Example 1 was changed to polymers B to D, respectively.

[Example 5]
70 parts of polymer F and 15 parts of fumed silica having a specific surface area of 200 m ² / g were uniformly mixed and mixed under reduced pressure by heating at 150 ° C. for 2 hours. This was mixed with 8 parts of vinyltrimethoxysilane, 2 parts of diisopropoxytitanium bis (ethylacetoacetate) and 0.5 part of γ-aminopropyltriethoxysilane until uniform. Further, a composition was prepared by mixing 30 parts of α, ω-trimethylsiloxy-dimethyl-polysiloxane having a viscosity of 100 mm ² / s until uniform under reduced pressure.

[Example 6]
A composition was prepared in the same manner as in Example 1 except that the fumed silica having a specific surface area of 200 m ² / g in Example 1 was changed to calcium silicate.

[Example 7]
Except that the α, ω-trimethylsiloxy-dimethyl-polysiloxane having a viscosity of 100 mm ² / s in Example 1 was changed to the α, ω-trimethylsiloxy-dimethyl-polysiloxane having a viscosity of 10,000 mm ² / s. A composition was prepared in the same manner as in Example 1.

[Comparative Example 1]
A composition was prepared in the same manner as in Example 1 except that α, ω-trimethylsiloxy-dimethyl-polysiloxane having a viscosity of 100 mm ² / s in Example 1 was not used.

[Comparative Example 2]
A composition was prepared in the same manner as in Example 1 except that the polymer A in Example 1 was changed to the polymer E.

[Comparative Example 3]
A composition was prepared in the same manner as in Example 1 except that the polymer F in Example 5 was changed to the polymer G.

[Comparative Example 4]
Example The viscosity of 2 is 100mm ² / s α, ω- trimethylsiloxy - dimethyl - polysiloxane viscosity of 100mm ² / s α, ω- trimethylsiloxy - diphenyl dimethyl - All substituents attached to the polysiloxane (silicon atom The composition was prepared in the same manner as in Example 2 except that the ratio was changed to 25 mol%.

<Results of performance test>
The compositions obtained in the above Examples and Comparative Examples were applied on a coated plate (thickness 200 μm) in advance using an epoxy anticorrosive paint so that the cured film thickness would be 300 μm, and 23 ° C. It was cured for 7 days under the condition of 50% RH to obtain a test coated plate. These test coating plates were subjected to a suspension test on the coast of Kanagawa Prefecture at a depth of 1.5 m for 12 months. The state of adhesion of shellfish such as barnacles and seaweeds was observed, and the results are shown in Tables 1 and 2.

Claims (7)

(A) As a base polymer, the following general formula (1) and / or (2)

(In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group, but does not include a phenyl group. Further, 2 mol% or more of R is a substituted or unsubstituted alkenyl group. X is an oxygen atom or C is a divalent hydrocarbon group having 1 to 8 carbon atoms, and n is a number that makes the viscosity of this diorganopolysiloxane at 25 ° C. 100 to 1,000,000 mm ² / s.)

(In the formula, Y is a hydrolyzable group, a is 2 or 3, R is a substituted or unsubstituted monovalent hydrocarbon group, but does not contain a phenyl group. Also, 2 mol% of R The above is a substituted or unsubstituted alkenyl group, X is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, and n is a viscosity of the diorganopolysiloxane at 25 ° C. of 100 to 1,000,000. 000 mm ² / s.)
Diorganopolysiloxane represented by
(B) A silane having two or more hydrolyzable groups in one molecule and / or a partially hydrolyzed condensate thereof, and (C) a silicone oil having no phenyl group and no reactive group bonded to a silicon atom. An antifouling condensation-curable organopolysiloxane composition. (B) component is the following general formula (3)
R ¹ _b SiZ _4-b (3)
(In the formula, R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, Z is independently a hydrolyzable group, and b is an integer of 0 to 2.)
The antifouling condensation-curable organopolysiloxane composition according to claim 1, wherein the composition is a silane and / or a partial hydrolysis-condensation product thereof. (C) Component is dimethyl polysiloxane oil and / or diethyl polysiloxane oil, The antifouling condensation curable organopolysiloxane composition of Claim 1 or 2 characterized by the above-mentioned. The antifouling condensation-curable organopolysiloxane composition according to any one of claims 1 to 3 , further comprising hydrophilic silica having a BET specific surface area of 10 m ² / g or more as a filler. . The antifouling condensation-curable organopolysiloxane composition according to any one of claims 1 to 3 , further comprising any one of calcium carbonate, calcium silicate, and silica zeolite as a filler. The viscosity ratio at 25 ° C. of the diorganopolysiloxane of component (A) and the diorganopolysiloxane of component (C) (viscosity of component (C) / viscosity of component (A)) is 0.02 to 10. Item 6. The antifouling condensation curable organopolysiloxane composition according to any one of Items 1 to 5 . An underwater structure coated with the composition according to any one of claims 1 to 6 .