JP4829583B2 - Method for producing room temperature curable organopolysiloxane composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a room temperature-hardening organopolysiloxane composition which has appropriate thixotropy before hardening and gives a highly hard hardened product and a coating film after hardening. <P>SOLUTION: In the method of manufacturing the above-mentioned composition containing an organopolysiloxane I which is a condensation product of an organopolysiloxane A containing M and Q units at a molar ratio (M/Q) of 0.6-1.2, having optionally D and T units respectively in 1.0 mole or less per 1 mole of the Q unit, less than 2.0 mass% of SiOH group, and an organopolysiloxane B terminal-sealed with a functional group-containing silyl group; a silane compound II having two or more silicon atom-bonded hydrolytic groups and/or its partial hydrolytic condensate; a filler III; a catalyst IV and a solvent V; a mixture is obtained by mixing B with III, the mixture is mixed with the solvent V of A, A and B are condensed in the presence of IV to obtain I-containing mixture, and the mixture is mixed with II to obtain the composition. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a room temperature curable organopolysiloxane composition having an appropriate thixotropy before curing and giving a high-strength cured product and a coating film after curing, as a coating material composition , Especially coatings for electrical and electronic parts and circuits, sealing agents for liquid crystal display elements, and paints that give antifouling coatings that coat underwater structures and prevent the attachment and growth of aquatic organisms on the surface (In this specification, “underwater structure” refers to a ship, a port facility, a buoy, a pipeline, a bridge, a submarine base, and the like.) , Subsea oil field drilling equipment, power station conduit pipes, aquaculture nets, stationary nets, etc.).

  Conventionally, various types of room temperature-curable silicone rubber coating material compositions that give rubber-like elastic bodies at room temperature are known. A cured film obtained from a room temperature curable silicone rubber coating material composition has excellent weather resistance, durability, cold resistance and the like compared to other organic rubbers, and is used in various fields, particularly in construction. In the field, it is widely used as a coating material for buildings, plants, water pipe inner surfaces, water pipe outer surfaces and the like. In recent years, the composition has been used as an environmental safety alternative to antifouling paints containing toxic antifouling agents such as tributyltin and cuprous oxide as a measure to prevent the attachment and growth of aquatic organisms on underwater structures. It has come to be widely used as an excellent coating material. Furthermore, the composition is often used from the viewpoints of heat resistance, adhesion, adhesion reliability, etc., as a coating agent for electric / electronic parts.

  Until now, the prevention of adhesion and growth of aquatic organisms has been mainly studied as a coating material for underwater structures. For example, liquid paraffin, petrolatum, liquid paraffin / petrolatum mixture is blended for the purpose of reducing the surface tension of the coating (Patent Document 1, Patent Document 2), amino group, carboxyl group, epoxy group and hydroxyl-terminated polyoxyethylene A silicone resin in which a polar group selected from a group is bonded to a silicon atom via a divalent aliphatic hydrocarbon (Patent Document 3), and at the molecular end of the silicon atom via an ethylene oxide or propylene oxide group The use of a silicone resin having an alkoxy group has been proposed (Patent Document 4). However, in recent years, in the field of underwater structures, particularly ship coatings, the physical strength of cured coatings has become necessary in order to improve durability during travel and prevent damage to the coating during berthing. Further, since it is applied not only to the horizontal portion but also to the vertical surface and the inclined surface, it is required to have thixotropy in order to prevent dripping.

  Also in the electric / electronic field, high strength is required for the coating itself as the circuit design has been further refined recently. Furthermore, it is required to have an appropriate thixotropy in order to prevent the coating film from flowing out and spreading to an inappropriate part after application.

Conventionally, (I) component (condensation reaction product of (A) component and (B) component), (II) component, (III) component, (IV) component, and (V) component are individually added in the present invention. The room temperature curable organopolysiloxane coating material composition is known, but its strength is insufficient for the above-mentioned use. The inventors have previously found that a room temperature-curable organopolysiloxane composition obtained by previously condensing the components (A) and (B) and further adding the component (II) is effective for increasing the strength. (Patent Document 5). In order to impart thixotropy to the present composition, a filler such as fumed silica is added as a standard method. However, since the component (A) is a solid at room temperature, it is usually handled in a state dissolved in the component (V). As a result, the condensation reaction product of the components (A) and (B) is also dissolved in the component (V). It is taken out. Since the condensation reaction product of the components (A) and (B) dissolved in the component (V) has a low viscosity, it is difficult to stir by applying a high shear stress. As a result, it was difficult to obtain a composition having uniform and good thixotropy due to poor dispersion of component (III). In addition, the non-uniform composition caused problems such as a decrease in strength and abnormal appearance.
JP 58-13673 A JP-A 62-84166 Japanese Patent No. 2503986 Japanese Patent No. 2952375 JP 2004-143331 A

  In view of the above prior art, the present invention has an appropriate thixotropy even in a solvent diluted state before curing, and gives a cured product and a coating film having high strength after curing. Is suitable as a ship coating material, and also provides a method for producing a room temperature curable organopolysiloxane composition suitable for use as a coating agent for electrical and electronic parts or circuits and a sealing agent for liquid crystal display elements. To do.

As a result of intensive studies aimed at achieving the above object, the present inventors have completed the present invention. That is, the present invention
(I) 100 parts by mass of an organopolysiloxane which is a condensation reaction product of 100 parts by mass of the following component (A) and 1 to 200 parts by mass of the component (B),
(A) R ₃ SiO _1/2 units (wherein R independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms) and SiO _4/2 units, and SiO _{4 / The} number of moles of R ₃ SiO _1/2 units per mole of ₂ units is 0.6 to 1.2 moles, and further R ₂ SiO _2/2 units and RSiO _3/2 units (wherein R is as defined above) Each of which may have 1.0 mol or less relative to 1 mol of SiO _4/2 units, and an organopolysiloxane having less than 2.0% by mass of hydroxy groups bonded to silicon atoms,
(B) a diorganopolysiloxane whose molecular chain end is blocked with a functional group-containing silyl group,
(II) a silane compound having two or more hydrolyzable groups bonded to a silicon atom in one molecule and / or a partial hydrolysis condensate thereof 0.1 to 30 parts by mass,
(III) Filler 1 to 500 parts by mass,
In the method for producing a room temperature curable organopolysiloxane composition comprising (IV) 0.05 to 3.0 parts by mass of a catalyst and (V) 10 to 1000 parts by mass of a solvent,
(1) Mixing component (B) and component (III) to obtain a mixture,
(2) A solution of the component (A) containing the component (V) as a solvent is mixed with the mixture, and the components (A) and (B) are subjected to a condensation reaction in the presence of the component (IV). ) To obtain a mixture containing the ingredients,
(3) Provided is a method for producing the room temperature-curable organopolysiloxane composition, wherein the mixture obtained in step (2) and the component (II) are mixed to obtain the composition. is there.

  The room temperature curable organopolysiloxane composition of the present invention has an appropriate thixotropy before curing, and gives a cured product having a high strength after curing, a coating film, and is used as a coating material composition. Particularly, it is suitable for use as a coating agent for electric / electronic parts or circuits, a sealing agent for liquid crystal display elements, and an antifouling paint for underwater structures.

  Hereinafter, the present invention will be described in detail. In the present invention, “room temperature” usually means 0 to 40 ° C., preferably 10 to 30 ° C.

[(I) component]
Component (I) is an organopolysiloxane that is a condensation reaction product of 100 parts by mass of the following component (A) and 1 to 200 parts by mass of component (B). As described above, component (I) is obtained by subjecting component (A) and component (B) to a condensation reaction in the presence of component (IV) in step (2) of the production method of the present invention.

[(A) component]
Component (A) includes R ₃ SiO _1/2 units (wherein R independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms) and SiO _4/2 units, The number of moles of R ₃ SiO _1/2 unit relative to 1 mole of Si0 _4/2 units is 0.6 to 1.2 moles. Furthermore, R ₂ SiO _2/2 units and RSiO _3/2 units (wherein R is Each of which is 1.0 mol or less per 1 mol of SiO _4/2 units, and is an organopolysiloxane having less than 2.0 mass% of hydroxy groups bonded to silicon atoms. (A) A component may be used individually by 1 type, or may be used in combination of 2 or more type.

  Examples of R include, for example, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, tert-butyl groups, pentyl groups, hexyl groups and other alkyl groups; cyclopentyl groups, cyclohexyl groups, etc. Cycloalkyl group; vinyl group, allyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group and other alkenyl groups; phenyl group and other aryl groups; chloromethyl group, 3-chloropropyl group, 1-chloro-2 Examples include halogenated alkyl groups such as -methylpropyl group and 3,3,3-trifluoropropyl group, among which methyl group, vinyl group and phenyl group are preferable, and methyl group is particularly preferable.

The organopolysiloxane itself as the component (A) can be obtained as a solution in an organic solvent by co-hydrolyzing and condensing an alkoxy group-containing silane compound corresponding to each unit in an organic solvent by a known method. For example, R ₃ SiOMe and Si (OMe) ₄ may be cohydrolyzed and condensed in an organic solvent together with R ₂ Si (OMe) ₂ and / or RSi (OMe) ₃ if desired (note that In the above formulas, R is as described above, and Me represents a methyl group). As the organic solvent, those capable of dissolving organopolysiloxane produced by cohydrolysis / condensation reaction are preferable, and typically, toluene, xylene, isooctane, naphtha mineral spirit, isoparaffin and the like can be mentioned. Further, the molar ratio of each unit contained in the component (A) can be appropriately set by adjusting, for example, the charged molar ratio of the methoxysilane compound corresponding to each unit.

The number of moles of the R ₃ SiO _1/2 unit relative to 1 mole of SiO _4/2 units in component (A) is in the range of 0.6 to 1.2 moles, preferably in the range of 0.65 to 1.15 moles. When the number of moles is less than 0.6 mole, the cured product of the resulting composition tends to have insufficient strength, and when it exceeds 1.2 moles, the cured product tends to be inferior in transparency.

Further, if desired, the content of each of the R ₂ SiO _2/2 units and RSiO _3/2 units that may be contained in the component (A) is 1.0 mol or less with _{respect to} 1 mol of SiO _4/2 units, Preferably it is 0.2-0.8 mol. When each content exceeds 1.0 mol, the cured product tends to be inferior in transparency.

  When the component (A) is prepared by cohydrolysis or condensation reaction, a hydroxy group bonded to a silicon atom is generated in the component (A). It is necessary for the condensation reaction between the component (A) and the component (B) that the component (A) contains this hydroxy group. The content of the component (A) as a whole is less than 2.0% by mass, and the lower limit is preferably 0.1% by mass. The content is particularly preferably 0.2 to 1.8% by mass. The hydroxy group content can be set by adjusting cohydrolysis and condensation reaction conditions. When the content is 2.0% by mass or more, the cured product of the resulting composition tends to have too high hardness, and its rubber elasticity tends to be impaired. Moreover, when the content is too small, the cured product may have insufficient strength.

[(B) component]
The component (B) to be subjected to a condensation reaction with the component (A) is a diorganopolysiloxane having a molecular chain terminal blocked with a functional group-containing silyl group. (B) A component may be used individually by 1 type, or may be used in combination of 2 or more type. As the component (B), the following general formula (1):

（式中、R¹は独立に非置換または置換の炭素原子数１〜10の１価炭化水素基であり、Ｘは独立に官能基であり、ａは１〜３の整数であり、ｎは10以上の整数である）で表されるジオルガノポリシロキサンを用いることが好ましい。

Wherein R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X is independently a functional group, a is an integer of 1 to 3, and n is It is preferable to use a diorganopolysiloxane represented by the following formula.

Examples of R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, Alkyl groups such as decyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group; phenyl group, tolyl group, xylyl group, Aryl groups such as naphthyl group; aralkyl groups such as benzyl group, phenethyl group and phenylpropyl group; chloromethyl group, 3-chloropropyl group, 1-chloro-2-methylpropyl group, 3,3,3-trifluoropropyl And a halogenated alkyl group such as a group. Among them, a methyl group is preferable.

  The functional group X which is a terminal group of the diorganopolysiloxane is not particularly limited as long as it undergoes a condensation reaction with the hydroxy group bonded to the silicon atom of the component (A). For example, the hydroxy group; Groups, ethoxy groups, propoxy groups, butoxy groups, etc .; methoxyethoxy groups, ethoxyethoxy groups, methoxypropoxy groups, etc .; alkoxyalkoxy groups; vinyloxy groups, isopropenyloxy groups, isobutenyloxy groups, etc. A ketoxime group such as a dimethyl ketoxime group, a methyl ethyl ketoxime group, a diethyl ketoxime group and a cyclohexanoxime; an acyloxy group such as an acetoxy group, a propionyloxy group, a butyryloxy group, an octanoyloxy group and a benzoyloxy group; N, N- Dimethylaminoxy group Amino group such as N, N-diethylaminoxy group; amino group such as dimethylamino group, diethylamino group, butylamino group, cyclohexylamino group; N-methylacetamide group, N-ethylacetamide group, N-methylbenzamide group, etc. And hydrolyzable groups such as amide groups, among which hydroxy groups and alkoxy groups are preferable, and hydroxy groups are particularly preferable.

  In the above formula, n is an integer of 10 or more, and the diorganopolysiloxane has a viscosity at 25 ° C. of not more than 500,000 mPa · s, preferably 50 to 200,000 mPa · s. preferable.

  Specific examples of the diorganopolysiloxane represented by the general formula (1) include, for example, molecular chain both-end silanol group-blocked dimethylpolysiloxane, molecular chain both-end silanol group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, Molecular chain both ends trimethoxysiloxy group-blocked dimethylpolysiloxane, molecular chain both ends trimethoxysiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends methyldimethoxysiloxy group-blocked dimethylpolysiloxane, molecular chain both ends tri Examples thereof include ethoxysiloxy group-blocked dimethylpolysiloxane. These can be used alone or in combination of two or more.

  (B) The compounding quantity of a component is 1-200 mass parts with respect to 100 mass parts of said (A) component, Preferably it is the range of 5-150 mass parts. If the blending amount is less than 1 part by mass, the cured product of the resulting composition tends to have high strength, so that it is difficult to have rubber elasticity, and if it exceeds 200 parts by mass, rubber elasticity tends to be impaired in this case as well. .

[(II) component]
The component (II) is a silane compound having an average of two or more hydrolyzable groups bonded to a silicon atom and / or a partial hydrolysis condensate thereof. (II) A component may be used individually by 1 type, or may be used in combination of 2 or more type. Examples of the hydrolyzable group include those other than the hydroxy group among the groups exemplified for X in the general formula (1) according to the component (B).

  Specific examples of the component (II) include, for example, methyltris (dimethylketoxime) silane, methyltris (methylethylketoxime) silane, ethyltris (methylethylketoxime) silane, methyltris (methylisobutylketoxime) silane, vinyltris (methylethylketoxime) silane, etc. Ketoxime silanes; alkoxysilanes such as methyltrimethoxysilane and vinyltrimethoxysilane; alkenoxysilanes such as methyltriisopropenoxysilane and vinyltrisisopropenoxysilane; methyltriacetoxysilane and vinyltriacetoxysilane Various silanes such as acetoxysilane; and hydrolytic condensates thereof. These can be used singly or in combination of two or more.

  Component (II) is blended in an amount of 0.1 to 30 parts by weight, preferably 1 to 15 parts by weight per 100 parts by weight of component (I). When the blending amount is less than 0.1 parts by mass, sufficient crosslinking and curing are unlikely to occur in the resulting composition, so that it is difficult to obtain a cured product having rubber elasticity from the composition, and when it exceeds 30 parts by mass, it is obtained from the composition. The resulting cured product tends to be inferior in mechanical properties.

[(III) component]
The component (III) is a filler. This component imparts moderate thixotropy to the material, and has the effect of adjusting dripping and spreading. (III) A component may be used individually by 1 type, or may be used in combination of 2 or more type.

  In the production method of the present invention, a filler used in an ordinary condensation-curable organopolysiloxane composition is suitably used as the component (III). Specifically, silicon dioxide powder such as fumes untreated silica, fumes treated silica, dry silica, wet silica, ground silica; untreated colloidal calcium carbonate, treated colloidal calcium carbonate, untreated heavy calcium carbonate, treated heavy Examples include calcium carbonate; metal oxides such as alumina, zinc oxide, titanium oxide, and iron oxide; metal carbonates such as zinc carbonate and magnesium carbonate; metal hydroxides such as aluminum hydroxide and calcium hydroxide. From the viewpoint of imparting thixotropy, fumed silica, dry silica, and colloidal calcium carbonate are particularly preferable.

  (III) The compounding quantity of a component is 1-500 mass parts with respect to 100 mass parts of said (I) component, Preferably it is the range of 1-100 mass parts. When the blending amount is less than 1 part by mass, it is difficult to obtain a composition having sufficient thixotropy, and when it exceeds 500 parts by mass, the resulting composition tends to increase in viscosity and tends to be inferior in coatability.

[(IV) component]
In the condensation reaction between the component (A) and the component (B), it is preferable to use a condensation reaction catalyst. The component (IV) is such a condensation reaction catalyst. (IV) A component may be used individually by 1 type, or may be used in combination of 2 or more type.

  Examples of the component (IV) include a tin compound, an amine compound, an alkali metal compound, and the like, and preferably an amine compound, specifically, ethylamine, propylamine, isopropylamine, butylamine, diethylamine, di-amine, and the like. Examples include butylamine, triethylamine, tetramethylguanidine, tetramethylethylenediamine, and the like.

  The amount of component (IV) used is not particularly limited as long as it is an effective amount as a catalyst, but is usually about 0.05 to 3.0 parts by mass with respect to 100 parts by mass of component (I). Further, the condensation reaction temperature is not particularly limited, but is usually in the range of 1 to 120 ° C, preferably 10 to 80 ° C. The reaction time is not particularly limited, but usually 30 minutes to 8 hours is sufficient.

[(V) component]
The component (V) is a solvent. The component (V) has an effect of imparting an appropriate viscosity to the resulting composition and adjusting workability during coating. (V) A component may be used individually by 1 type, or may be used in combination of 2 or more type.

  In the production method of the present invention, a solvent used for an ordinary condensation-curable organopolysiloxane composition is preferably used. Specifically, saturated hydrocarbons such as pentane, hexane, heptane, octane and isooctane; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate; ethanol, Examples include alcohols such as isopropanol; low-molecular cyclic siloxanes such as octamethylcyclotetrasiloxane; isoparaffins and the like. The component (V) may be the same as or different from the organic solvent used during the co-hydrolysis for preparing the component (A).

  (V) The compounding quantity of a component is 10-1000 mass parts with respect to 100 mass parts of said (I) component, Preferably it is the range of 50-500 mass parts. When the blending amount is less than 10 parts by mass, it is difficult to obtain a composition having sufficient workability, and when it exceeds 1000 parts by mass, the film thickness of the coating film produced from the resulting composition tends to be lowered, and the coating film is strong. It tends to be inferior.

[(VI) component and (VII) component]
In the composition obtained by the production method of the present invention, if necessary, in addition to 3 parts by mass of (VI) all monovalent groups bonded to silicon atoms, relative to 100 parts by mass of component (I). 1 to 200 parts by mass of an organopolysiloxane in which the molecular chain terminal is blocked with a trialkylsiloxy group and / or a functional group-containing silyl group, or (VII) 1 to 200 parts by mass of an organopolysiloxane with an HLB value of 1 to 8 that contains a group having an oxyalkylene structure and whose molecular chain ends are blocked with a trialkylsiloxy group and / or a functional group-containing silyl group May be. All of these components are preferably blended especially when the composition is applied to an antifouling paint for underwater structures. When the component (V) or (VI) is blended, the performance of preventing adhesion and growth of aquatic organisms on the cured coating film obtained from the composition is likely to be improved. (VI) component or (VII) component may be used individually by 1 type, or may be used in combination of 2 or more type.

  As the component (VI), the following general formula (2):

（式中、Ｒ'は独立にフェニル基またはメチル基、Ｒ²は独立に非置換または置換の炭素原子数１〜10のフェニル基以外の１価炭化水素基、Ｒ³は独立に炭素原子数１〜８のアルキル基であり、Ｙは独立に官能基であり、ｂは０〜３の整数であり、ｐおよびｑは１以上の整数であり、ただし、ｐ＋ｑの和は10以上の整数であり、かつ、ｐはケイ素原子に結合した全ての一価の基においてフェニル基の含有量が3〜50モル％となる数である）
で表されるオルガノポリシロキサンを用いることが好ましい。ｐ＋ｑの和は、10以上の整数であることに加え、上記一般式（２）で表されるオルガノポリシロキサンの25℃における粘度が20〜5000ｍｍ²/sとなる数の範囲とすることがよい。

Wherein R ′ is independently a phenyl group or a methyl group, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group other than a phenyl group having 1 to 10 carbon atoms, and R ³ is independently the number of carbon atoms. 1 to 8 alkyl groups, Y is independently a functional group, b is an integer of 0 to 3, p and q are integers of 1 or more, provided that the sum of p + q is an integer of 10 or more And p is a number such that the content of the phenyl group is 3 to 50 mol% in all monovalent groups bonded to the silicon atom)
It is preferable to use an organopolysiloxane represented by: In addition to being an integer of 10 or more, the sum of p + q is preferably in a range of numbers in which the viscosity at 25 ° C. of the organopolysiloxane represented by the general formula (2) is 20 to 5000 mm ² / s. .

Examples of R ² include groups other than the phenyl group among the groups exemplified for R ¹ of the general formula (1) relating to the component (B). As said R < ³ >, the C1-C8 alkyl group can be mentioned among the groups illustrated about R < ¹ > of General formula (1) which concerns on the said (B) component. Examples of the functional group for Y include groups other than the hydroxy group among the groups exemplified for X in the general formula (1) according to the component (B).

  If the content of the phenyl group in the component (VI) is too small, the component tends to be more compatible with other components, so that it is difficult to bleed out from the resulting cured product. Tends to be quickly separated from the cured product because compatibility tends to deteriorate, and in any case, the effect of preventing adhesion of aquatic organisms by the cured product may be insufficient.

  Specific examples of the component (VI) include phenyl group-containing silicone oils such as a trimethylsiloxy group-capped methylphenylsiloxane / dimethylsiloxane copolymer at both terminals and a triphenylsiloxy group-capped diphenylsiloxane / dimethylsiloxane copolymer at both terminals. Etc. These can be used singly or in combination of two or more.

  As said (VII) component, following General formula (3):

（式中、Ｒ⁴は独立に非置換または置換の炭素原子数１〜10の１価炭化水素基であり、Ｒ⁵は独立に炭素原子数１〜８のアルキル基であり、Ｐは独立にポリオキシアルキレン構造を有する１価の基であり、Ｚは独立に官能基であり、ｃは０〜３の整数であり、ｍは１以上、好ましくは２〜10の整数、ｎは１以上好ましくは10〜1000の整数であり、ｍ＋ｎの和は10以上の整数である）で表される構造を有し、ＨＬＢ値が１〜８、好ましくは２〜７のオルガノポリシロキサンを用いることが好ましい。ｍ＋ｎの和は、10以上の整数であることに加え、25℃における粘度が20〜5000ｍｍ²/sとなる数の範囲とすることがよい。

Wherein R ⁴ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁵ is independently an alkyl group having 1 to 8 carbon atoms, and P is independently A monovalent group having a polyoxyalkylene structure, Z is independently a functional group, c is an integer of 0 to 3, m is an integer of 1 or more, preferably an integer of 2 to 10, and n is 1 or more. Is an integer of 10 to 1000, and the sum of m + n is an integer of 10 or more), and an organopolysiloxane having an HLB value of 1 to 8, preferably 2 to 7 is preferably used. . In addition to being an integer of 10 or more, the sum of m + n is preferably in a range of numbers where the viscosity at 25 ° C. is 20 to 5000 mm ² / s.

Examples of R ⁴ include the groups exemplified for R ^{1 in the} general formula (1) relating to the component (B). As said R < ⁵ >, the C1-C8 alkyl group can be mentioned among the groups illustrated about R < ¹ > of General formula (1) which concerns on the said (B) component. Examples of the functional group of Z include those other than the hydroxy group among the groups exemplified for X in the general formula (1) relating to the component (B).

Examples of the group having a polyoxyalkylene structure of P include, for example, the following formula (4):
_{-O (C s H 2s O)} u R 6 (4)
Wherein R ⁶ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, s is an integer of 1 to 8, preferably 2 to 4, and u is 1 to 30, preferably Is an integer of 2 to 25, provided that when there are a plurality of P in component (VII), R ⁶ , s and u may be the same or different for each P). It can be illustrated. Examples of R ⁶ include the groups exemplified for R ^{1 in the} general formula (1) relating to the component (B). Specific examples of P include groups having a structure such as polyoxyethylene, polyoxypropylene, and polyoxytetramethylene, and polyoxyethylene (ethylene oxide) and polyoxypropylene (propylene oxide) are preferable.

  Even if the HLB value of the component (VII) is too small or too large, the effect of preventing adhesion of aquatic organisms by the resulting cured coating film may be insufficient.

  Specific examples of the component (VII) include, for example, side chain and / or both terminal and / or one terminal polyether-modified silicone oil, and the polymer terminal group is a silanol group, a trimethylsiloxy group, a trimethoxysiloxy group. , Triethoxysiloxy group, methyldimethoxysiloxy group, methyldi (methylethylketoxime) siloxy group, and the like. These can be used singly or in combination of two or more.

[Other ingredients]
A curing catalyst may be blended in the composition obtained by the production method of the present invention, if necessary. Examples of the curing catalyst include organic titanium compounds such as tetraisopropoxy titanium, tetrabutoxy titanium, and titanium bisacetylacetonate; strong bases such as tetramethylguanidylpropyltrimethoxysilane and γ-aminopropyltriethoxysilane; Zinc acid, lead 2-ethylhexanoate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, zinc naphthenate, ferrous octoate, etc. Is mentioned. When blending this curing catalyst, the blending amount may be an effective amount as a catalyst and is not particularly limited, but is usually 0.01 to 20 parts by weight, preferably 0.05 to 10 parts per 100 parts by weight of the component (I). About mass parts.

  In addition to the above components, generally known additives and the like may be added to the composition of the present invention. Additives include thixotropy improvers such as polyethers; physiologically active substances such as fungicides, antibacterial agents, and algae inhibitors; adhesion aids such as γ-aminopropyltriethoxysilane, 3- [2- And aminosilanes such as (aminoethylamino) propyl] trimethoxysilane and epoxysilanes such as γ-glycidylpropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

[Production method]
Specifically, the method for producing the room temperature curable organopolysiloxane composition of the present invention includes:
Step (1): A step of mixing the component (B) and the component (III) to obtain a mixture,
Step (2): A solution of the component (A) using the component (V) as a solvent is mixed with the mixture, and the components (A) and (B) are subjected to a condensation reaction in the presence of the component (IV). (I) The process of obtaining the mixture containing a component, and the process (3): The process of mixing this mixture obtained by the process (2) and (II) component, and obtaining the said composition is included.

・ Process (1)
Step (1) is achieved, for example, by kneading component (B) and component (III) with a generally known mixer. As the mixer, for example, a planetary mixer, a mixer using planetary rotors such as Shinagawa mixer, etc .; a static mixer such as a static mixer; a strong shear force such as a three-roll mill or a hensil mixer if necessary Can be used. Although depending on the type of component (III), the mixing temperature is, for example, 0 ° C to 200 ° C, usually in the range of room temperature to 150 ° C, and the mixing time is, for example, 15 minutes to 6 hours, usually 30 minutes to 3 It is a range of time.

・ Process (2)
Step (2) can also be achieved by the above-mentioned mixer. (A) component solution (hereinafter referred to as “(A) component (V) solution”) using the component (V) as a solvent in the mixture obtained in step (1) in the same mixer. IV) The component may be mixed. Alternatively, once the mixture obtained in the step (1) is taken out from the mixer and put into another mixer, the (V) solution of the component (A) and the component (IV) are mixed with the mixture. Also good. The component (A) solution (V) and the component (IV) may be added simultaneously to the mixture obtained in the step (1). Usually, however, first, the mixture obtained in the step (1) is added to the mixture obtained in the step (1). It is desirable to add and mix the (V) solution of component (A) and then add and mix component (IV) to subject the components (A) and (B) to a condensation reaction. Depending on the type of component (V), the mixing temperature is, for example, 0 to 100 ° C., usually in the range of room temperature to 60 ° C., and the mixing time is, for example, 15 minutes to 6 hours, usually 1 to 2 hours. It is a range of time.

・ Process (3)
Step (3) can also be achieved by the above-mentioned mixer. Although depending on the type of component (II), the mixing temperature is, for example, 0 ° C to 100 ° C, usually in the range of room temperature to 60 ° C, and the mixing time is, for example, 15 minutes to 6 hours, usually 30 minutes to 2 It is a range of time. In the step (3), in order to avoid contact between the resulting composition and moisture in the air, after purging with a dry gas such as dry air or dry nitrogen, the dry gas is flowed It is desirable to mix with

-Addition of optional component The component (VI) or the component (VII) can be mixed into the reaction system at at least one point in the period from the start of the step (1) to the end of the step (3). Here, the reaction system means the component (B) and the component (III) at the start of the step (1), and in the period from the start of the step (1) to the end of the step (3), In the period after the completion of the step (3), it means the obtained composition. That is, the component can be mixed with the component (B) and the component (III) at the start of the step (1), and / or the period from the start of the step (1) to the end of the step (3) Can be mixed with the mixture at that time and / or at least one time after the end of step (3) with the composition. Usually, at least at one point in the period after completion of the step (3), the component (VI) or the component (VII) is added to the obtained composition and kneaded by using the above-mentioned mixer. The component can be added to the composition obtained by the production method of the invention.

  Components other than the components (I) to (VII) can be added to the composition obtained by the production method of the present invention in the same manner as described above for the components (VI) or (VII).

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in full detail, this invention is not limited by these Examples. Unless otherwise stated, operations were performed at room temperature.

[Example 1]
50 parts by mass of dimethylpolysiloxane with a viscosity of 20000 mPa · s sealed at 25 ° C. with silanol groups at both ends and 5 parts by mass of fumed silica with a specific surface area of 130 m ² / g surface-treated with dimethyldichlorosilane And a homogeneous mixture was obtained. This mixture consists of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, (CH ₃ ) ₃ SiO _1/2 units / SiO ₂ units (molar ratio) = 0.75, containing hydroxy groups bonded to silicon atoms 100 parts by mass of a 50% by mass toluene solution of an organopolysiloxane having an amount of 1.1% by mass and 0.2 parts by mass of tetramethylguanidine were added and mixed with stirring at room temperature for 1 hour. Next, 12 parts by mass of vinyltrismethylethylketoxime silane was added to the resulting mixture, and mixed for 30 minutes under a dry nitrogen atmosphere to obtain Composition 1.

[Comparative Example 1]
50 parts by mass of dimethylpolysiloxane having a viscosity at 25 ° C. of which both ends are blocked with silanol groups and having a viscosity of 20000 mPa · s, is composed of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, and (CH ₃ ) ₃ SiO _1/2 unit / SiO ₂ unit (molar ratio) = 0.75, 100 mass parts of 50 mass% toluene solution of organopolysiloxane having a hydroxy group content of 1.1 mass% bonded to silicon atoms, and 0.2 mass of tetramethylguanidine A part by mass was added and stirred and mixed at room temperature for 1 hour. Next, 5 parts by mass of fumed silica having a specific surface area of 130 m ² / g surface-treated with dimethyldichlorosilane was mixed with the obtained mixture. Furthermore, 12 parts by mass of vinyltrismethylethylketoxime silane was added to the obtained mixture and mixed for 30 minutes in a dry nitrogen atmosphere to obtain composition 2.

[Comparative Example 2]
50 parts by mass of dimethylpolysiloxane with a viscosity of 20000 mPa · s sealed at 25 ° C. with silanol groups at both ends and 5 parts by mass of fumed silica with a specific surface area of 130 m ² / g surface-treated with dimethyldichlorosilane And a homogeneous mixture was obtained. This mixture consists of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, (CH ₃ ) ₃ SiO _1/2 units / SiO ₂ units (molar ratio) = 0.75, containing hydroxy groups bonded to silicon atoms 100 parts by mass of a 50% by mass toluene solution of an organopolysiloxane having an amount of 1.1% by mass was added and stirred at room temperature for 1 hour. Next, 12 parts by mass of vinyltrismethylethylketoxime silane was added to the obtained mixture and mixed for 30 minutes in a dry nitrogen atmosphere to obtain composition 3.

[Comparative Example 3]
50 parts by mass of dimethylpolysiloxane having a viscosity at 25 ° C. of which both ends are blocked with silanol groups and having a viscosity of 20000 mPa · s, is composed of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, and (CH ₃ ) ₃ SiO _1/2 unit / SiO ₂ unit (molar ratio) = 0.75, 100 mass parts of 50 mass% toluene solution of organopolysiloxane having a hydroxy group content of 1.1 mass% bonded to silicon atoms, and 0.2 mass of tetramethylguanidine A part by mass was added and stirred and mixed at room temperature for 1 hour. Next, 12 parts by mass of vinyltrismethylethylketoxime silane was added to the obtained mixture, and mixed for 30 minutes under a dry nitrogen atmosphere to obtain composition 4.

[Measurement 1]
Each composition obtained above was formed into a sheet having a thickness of 2 mm, and the sheet was left to cure in an atmosphere of 23 ± 2 ° C. and 50 ± 5% RH for 7 days. Each cured sheet was subjected to appearance confirmation and physical property measurement according to JIS K 6249. The results are shown in Table 1. Also, 1 g of each composition was applied on a glass plate, and the diameter of the spread was measured. The results are also shown in Table 1.

[Example 2]
50 parts by mass of dimethylpolysiloxane with a viscosity of 20000 mPa · s sealed at 25 ° C. with silanol groups at both ends and 5 parts by mass of fumed silica with a specific surface area of 130 m ² / g surface-treated with dimethyldichlorosilane And a homogeneous mixture was obtained. This mixture consists of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, (CH ₃ ) ₃ SiO _1/2 units / SiO ₂ units (molar ratio) = 0.75, containing hydroxy groups bonded to silicon atoms 100 parts by mass of a 50% by mass isoparaffin solution of organopolysiloxane having an amount of 1.0% by mass and 0.2 parts by mass of tetramethylguanidine were added and mixed with stirring at room temperature for 1 hour. Next, 10 parts by weight of methyltrismethylethylketoxime silane, 0.2 parts by weight of dioctyltin dilaurate and 1 part by weight of γ-aminopropyltriethoxysilane are added to the resulting mixture, and mixed for 30 minutes under a dry nitrogen atmosphere to give composition 5. Obtained.

[Example 3]
50 parts by mass of dimethylpolysiloxane with a viscosity of 5000 mPa · s sealed at 25 ° C at both ends with silanol groups and 5 parts by mass of fumed silica with a specific surface area of 200 m ² / g without treatment are decompressed at 120 ° C for 2 hours. Heat treatment was mixed to obtain a uniform mixture. This mixture consists of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, (CH ₃ ) ₃ SiO _1/2 units / SiO ₂ units (molar ratio) = 0.75, containing hydroxy groups bonded to silicon atoms 100 parts by mass of a 50% by mass isoparaffin solution of organopolysiloxane having an amount of 1.0% by mass and 0.2 parts by mass of tetramethylguanidine were added and mixed with stirring at room temperature for 1 hour. Next, 10 parts by mass of methyltrismethylethylketoxime silane, 0.2 parts by mass of dioctyltin dilaurate, and 1 part by mass of γ-aminopropyltriethoxysilane are added to the resulting mixture, and mixed for 30 minutes under a dry nitrogen atmosphere to obtain Composition 6. Obtained.

[Example 4]
50 parts by mass of dimethylpolysiloxane with a viscosity of 700 mPa · s at 25 ° C, both ends blocked with trimethoxysilyl groups, and 10 parts by mass of fumed silica with a specific surface area of 130 m ² / g surface-treated with dimethyldichlorosilane The mixture was heat-treated under reduced pressure at 150 ° C. for 2 hours to obtain a uniform mixture. This mixture consists of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, (CH ₃ ) ₃ SiO _1/2 units / SiO ₂ units (molar ratio) = 0.75, containing hydroxy groups bonded to silicon atoms 100 parts by mass of a 50% by mass isoparaffin solution of organopolysiloxane having an amount of 1.0% by mass and 0.5 parts by mass of tetramethylethylenediamine were added and mixed with stirring at room temperature for 2 hours. Next, 10 parts by mass of methyltrismethylethylketoxime silane, 0.1 part by mass of dibutyltin dioctoate and 1 part by mass of γ-aminopropyltriethoxysilane were added to the resulting mixture, and the mixture was mixed for 30 minutes in a dry nitrogen atmosphere. Got.

[Example 5]
50 parts by mass of dimethylpolysiloxane with a viscosity of 20000 mPa · s sealed at 25 ° C. with silanol groups at both ends and 5 parts by mass of fumed silica with a specific surface area of 130 m ² / g surface-treated with dimethyldichlorosilane And a homogeneous mixture was obtained. This mixture consists of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, (CH ₃ ) ₃ SiO _1/2 units / SiO ₂ units (molar ratio) = 0.75, containing hydroxy groups bonded to silicon atoms 100 parts by weight of a 50% by weight isooctane solution of an organopolysiloxane having an amount of 1.5% by weight and 0.2 parts by weight of tetramethylguanidine were added and mixed with stirring at room temperature for 1 hour. Next, 8 parts by mass of vinyltrisisopropenoxysilane and 1 part by mass of tetramethylguanidylpropyltrimethoxysilane were added to this mixture, and mixed for 30 minutes in a dry nitrogen atmosphere to obtain composition 8.

[Measurement 2]
Each composition obtained above was formed into a sheet having a thickness of 2 mm, and the sheet was left to cure in an atmosphere of 23 ± 2 ° C. and 50 ± 5% RH for 7 days. Each cured sheet was subjected to appearance confirmation and physical property measurement according to JIS K 6249. The results are shown in Table 2. Also, 1 g of each composition was applied on a glass plate, and the diameter of the spread was measured. The results are also shown in Table 2.

[Example 6]
In 100 parts by mass of the composition of Example 1, 5 mol% of phenyl groups are contained in all monovalent groups bonded to silicon atoms, the viscosity at 25 ° C. is 300 mPa · s, and both ends of the molecular chain are trimethylsiloxy. A composition 9 was obtained by uniformly mixing 15 parts by mass of a methylphenylsiloxane / dimethylsiloxane copolymer blocked with a group and 50 parts by mass of xylene.

[Comparative Example 4]
100 parts by mass of the composition of Comparative Example 2 contains 5 mol% of phenyl groups in all monovalent groups bonded to silicon atoms, the viscosity at 25 ° C. is 300 mPa · s, and both ends of the molecular chain are trimethylsiloxy. A composition 10 was obtained by uniformly mixing 15 parts by mass of a methylphenylsiloxane / dimethylsiloxane copolymer blocked with a group and 50 parts by mass of xylene.

[Example 7]
100 parts by mass of the composition of Example 1, containing a polyoxyethylene group in the side chain, a viscosity at 25 ° C. of 100 mPa · s, both ends of the molecular chain blocked with trimethylsiloxy groups, an HLB value of 2 20 parts by mass of dimethylpolysiloxane and 50 parts by mass of isoparaffin were uniformly mixed to obtain a composition 11.

[Comparative Example 5]
In 100 parts by mass of the composition of Comparative Example 3, the side chain contains a polyoxyethylene group, the viscosity at 25 ° C. is 100 mPa · s, both ends of the molecular chain are blocked with trimethylsiloxy groups, and the HLB value is 2. 20 parts by mass of dimethylpolysiloxane and 50 parts by mass of isoparaffin were uniformly mixed to obtain a composition 12.

[Measurement 3]
Each composition obtained above was applied to a steel plate with a thickness of 300 μm using a sag tester according to JIS K 5400, and immediately after that, the steel plate was held vertically to check the sagging property of each composition. The results are shown in Table 3. Furthermore, each composition was applied to a coated plate pre-coated with an epoxy-based anticorrosive paint (film thickness 200 μm) so that the cured film thickness would be 300 μm, and left to stand for 7 days in an atmosphere of 23 ° C. and 50% RH. A test coated plate was prepared. These test coated plates were fixed in the sea and tested for 12 months immersion. After 12 months, the test coating plate was pulled up, and the state of the coating film and the adhesion state of shellfish such as barnacles and seaweeds were visually evaluated. The results are also shown in Table 3.

[Example 8]
50 parts by mass of dimethylpolysiloxane with a viscosity of 700 mPa · s sealed at 25 ° C with silanol groups at both ends and 3 parts by mass of fumed silica with a specific surface area of 130 m ² / g surface-treated with dimethyldichlorosilane And a homogeneous mixture was obtained. This mixture consists of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, (CH ₃ ) ₃ SiO _1/2 units / SiO ₂ units (molar ratio) = 0.75, containing hydroxy groups bonded to silicon atoms 100 parts by weight of a 50% by weight isooctane solution of an organopolysiloxane having an amount of 1.5% by weight and 0.2 parts by weight of tetramethylguanidine were added and mixed with stirring at room temperature for 1 hour. Next, 8 parts by mass of phenyltrisisopropenoxysilane, 1 part by mass of tetramethylguanidylpropyltrimethoxysilane, 1 part by mass of γ-aminopropyltriethoxysilane, and 50 parts by mass of ethyl acetate were added to the resulting mixture and dried. A composition 13 was obtained by mixing for 30 minutes under a nitrogen atmosphere.

[Comparative Example 6]
50 parts by mass of dimethylpolysiloxane having a viscosity of 700 mPa · s at 25 ° C. with both ends blocked with silanol groups, consisting of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, (CH ₃ ) ₃ SiO _1/2 unit / SiO ₂ unit (molar ratio) = 0.75, 100 mass parts of 50 mass% isooctane solution of organopolysiloxane having a hydroxy group content of 1.5 mass% bonded to silicon atoms, and 0.2 mass of tetramethylguanidine A part by mass was added and stirred and mixed at room temperature for 1 hour. Next, 8 parts by mass of phenyltrisisopropenoxysilane, 1 part by mass of tetramethylguanidylpropyltrimethoxysilane, 1 part by mass of γ-aminopropyltriethoxysilane, and 50 parts by mass of ethyl acetate were added to the resulting mixture and dried. Composition 14 was obtained by mixing for 30 minutes in a nitrogen atmosphere.

[Measurement 4]
Each composition was applied onto a glass plate in a bead shape using a 2 mmφ nozzle, and the width of the spread was measured. The results are shown in Table 4. Further, a comb-shaped silver electrode having a line width of 100 μm and a distance between lines of 100 μm was coated to a thickness of 50 μm, and the insulation resistance value between the electrodes was measured after 168 hours of degradation at an applied voltage of 60 V, 60 ° C. and 80% RH. The results are also shown in Table 4.

Claims (3)

(I) 100 parts by mass of an organopolysiloxane which is a condensation reaction product of 100 parts by mass of the following component (A) and 1 to 200 parts by mass of the component (B),
(Wherein, R represents a monovalent hydrocarbon group or a halogenated alkyl group having 1 to 6 carbon atoms of 1 to 6 carbon atoms in Hi置conversion independently) (A) R ₃ SiO _1/2 units and SiO _4/2 units are included, and the number of moles of R ₃ SiO _1/2 units relative to 1 mole of SiO _4/2 units is 0.6 to 1.2 moles. Furthermore, R ₂ SiO _2/2 units and RSiO _3/2 units ( In each of the above formulas, each R may have 1.0 mol or less per mol of SiO _4/2 units, and each hydroxy group bonded to a silicon atom is 0.1% by mass or more and 2.0% by mass. Organopolysiloxane having less than,
(B) The following general formula (1):

(In the formula, R ¹ is a monovalent hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms having 1 to 10 carbon atoms in Hi置conversion independently, X is independently a hydroxy group or an alkoxy group A is an integer of 1 to 3, and n is an integer of 10 or more),
(II) a silane compound having two or more hydrolyzable groups bonded to a silicon atom in one molecule and / or a partial hydrolysis condensate thereof 0.1 to 30 parts by mass,
(III) Filler 1 to 500 parts by mass,
(IV) A catalyst effective amount, and (V) a method for producing a room temperature curable organopolysiloxane composition containing 10 to 1000 parts by mass of a solvent,
(1) Mixing component (B) and component (III) to obtain a mixture,
(2) A solution of the component (A) containing the component (V) as a solvent is mixed with the mixture, and the components (A) and (B) are subjected to a condensation reaction in the presence of the component (IV). ) To obtain a mixture containing the ingredients,
(3) The method for producing the room temperature-curable organopolysiloxane composition, wherein the composition obtained by mixing the mixture obtained in the step (2) and the component (II) is obtained. The room temperature curable organopolysiloxane composition further comprises:
(VI) Organopolysiloxane in which 3 to 50 mol% of all monovalent groups bonded to a silicon atom are phenyl groups and the molecular chain ends are blocked with trialkylsiloxy groups and / or functional group-containing silyl groups 1 2. The production method according to claim 1, comprising -200 parts by mass, wherein the (VI) component is mixed into the reaction system at at least one point in time from the start of step (1) to the end of step (3). . The room temperature curable organopolysiloxane composition further comprises:
(VII) Organopolysiloxane having an HLB value of 1 to 8 containing a group having a polyoxyalkylene structure and having a molecular chain terminal blocked with a trialkylsiloxy group and / or a functional group-containing silyl group 1 to 200 parts by mass wherein the manufacturing method according to claim 1 wherein (VII) component to be mixed into the reaction system at least one of the period from the start of step (1) until after the end of step (3).