Method for producing room temperature curable organopolysiloxane composition and end-capping agent

Abstract

To provide a method for producing a room temperature-curable organopolysiloxane composition which can be easily produced and has excellent preservability.SOLUTION: There is provided a method for producing a room temperature-curable organopolysiloxane composition which comprises (A) an organopolysiloxane in which the molecular chain terminals are blocked with a silanol group, (B-1) a hydrolyzable organosilane compound and / or a partially hydrolyzed product thereof, (B-2) a hydroxylamine compound, (B-3) an organic divalent tin compound and / or an organic tetravalent tin compound and (C) a specific amount of a curing catalyst, as required and comprises [i] a step of uniformly mixing a part or whole of the (B-1) and (B-3) with the whole of (B-2) to prepare a terminal blocking agent (B), [ii] a step of mixing (A) and (B) uniformly to prepare a mixture containing an organopolysiloxane in which the silanol group in (A) is blocked with the hydrolyzable organosilyl group in (B-1) and [iii] a step of blending the remainder of (B-1) and (B-3) and (C) as needed in the mixture.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing a room temperature curable organopolysiloxane composition (room temperature curable silicone resin composition) containing, as a starting material for a main agent (base polymer), an organopolysiloxane having a silicon atom bonded to a hydroxyl group (i.e., a silanol group) at a molecular chain end as a silicon group (hereinafter also referred to as a "reactive silicon group") that can be crosslinked by forming a siloxane bond. That is, a polymer having a main chain composed of a repeating unit of a diorganosiloxane unit blocked at the molecular chain end with a silanol group. and a terminal blocking agent It relates to this.

Background Art

[0002] Polymers having reactive silicon groups hydrolyze and condense in the presence of moisture. These polymers having reactive silicon groups can be crosslinked and cured in the presence of moisture and used as curable resin compositions. Among these polymers, those having a main chain composed of a silicon-containing compound (especially organopolysiloxane) are generally known as silicone polymers. The curable resin compositions using these have the characteristics of being liquid at room temperature and becoming a rubber elastic body by curing, and are widely used as coating agents, adhesives, building sealants, etc. by utilizing their characteristics as room temperature curable organopolysiloxane compositions. Room temperature curable organopolysiloxane compositions are often classified according to the compounds released from the composition when in contact with moisture in the air, and typical examples include deacetic acid type, deoxime type, deamide type, dehydroxylamine type, deacetone type, and dealcohol type organopolysiloxane compositions. Among them, the dealcohol type organopolysiloxane composition that cures by releasing alcohol is particularly preferably used because it has little odor, does not corrode metals such as copper and iron, is excellent in self-adhesion (adhesion after curing to various base materials without using a primer), and is excellent in adhesion durability.

[0003] In order to obtain a de-alcoholized organopolysiloxane composition, an organopolysiloxane preliminarily end-capped with an alkoxysilyl group is used as a base polymer, or an organopolysiloxane having a silanol group as a terminal functional group is used as a starting material and end-capped with a silane compound having an alkoxy group during the manufacturing process. In order to obtain ease of production and storage stability, it is preferable to use an organopolysiloxane preliminarily end-capped with an alkoxysilyl group, but it has disadvantages such as high cost. As a method for end-capping a silanol group during the manufacturing process, it is generally known to blend a basic silane compound such as an amino group-containing silane as an end-capping catalyst. In Japanese Patent No. 5888112 and Japanese Patent No. 6252466 (Patent Documents 1 and 2), it is exemplified that a basic silane compound having a guanidine group or a phenylmethanamine group is used as an end-capping catalyst. However, since the basic silane compound used as an end-capping catalyst is special, it may be economically disadvantageous, or depending on the composition, end-capping may be insufficient, resulting in problems such as rapid thickening and gelation during production.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention has been made in view of the above circumstances, and aims to provide a method for producing a room-temperature curable organopolysiloxane composition that is easy to produce and has excellent storage properties. and a terminal blocking agent for the purpose of providing.

Means for Solving the Problems

[0006] As a result of intensive studies to achieve the above object, the inventors of the present invention prepared a terminal blocking agent by uniformly mixing a hydrolyzable organosilane compound and / or its partial hydrolyzate, a hydroxylamine compound, and an organic divalent tin compound and / or an organic tetravalent tin compound. [ii] A terminal blocking step of mixing the terminal blocking agent with an organopolysiloxane having a silanol group at the terminal to block the terminal silanol group of the organopolysiloxane with a hydrolyzable silyl group. [iii] To the mixture obtained in the terminal blocking step, if there is a remainder in the hydrolyzable organosilane compound and / or its partial hydrolyzate, the remainder thereof, and if there is a remainder in the organic divalent tin compound and / or the organic tetravalent tin compound curing catalyst, the remainder thereof, and when a curing catalyst other than the hydroxylamine compound, the organic divalent tin compound, and the organic tetravalent tin compound is blended, the entire amount thereof. The inventors have found that a room temperature curable organopolysiloxane composition obtained by a production method including a step of mixing is easy to produce and has excellent storage stability, and thus have completed the present invention.

[0007] That is, the present invention provides a method for producing the following room temperature curable organopolysiloxane composition and a terminal blocking agent is provided. [1] (A) Organopolysiloxane having silanol groups blocking both ends and / or one end of the molecular chain: 100 parts by mass, (B-1) The following general formula (1) R 1 4-a Si(ОR 2 ) a (1) (In the formula, R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, R 2 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a is 3 or 4.) The hydrolyzable organosilane compound represented by and / or its partial hydrolyzate: 0.01 to 30 parts by mass, (B-2) Hydroxylamine compound: 0.01 to 10 parts by mass, (B-3) an organic divalent tin compound, or Organic divalent tin compound and and organicTetravalent tin compound: 0.001 to 20 parts by mass, and (C) Curing catalyst (excluding components (B-2) and (B-3)): 0 to 20 parts by mass A method for producing a room temperature curable organopolysiloxane composition containing [i]: A step of preparing a terminal blocking agent (B) by uniformly mixing in advance a part or all of the component (B-1), all of the component (B-2), and a part or all of the component (B-3) (however, components (A) and (C) are not included during step [i]), [ii]: A step of uniformly mixing the component (A) and the component (B) obtained in step [i] to obtain a mixture containing an organopolysiloxane in which the silanol groups at the molecular chain ends of the organopolysiloxane of the component (A) are blocked with hydrolyzable organosilyl groups (-SiR 1 4-a (ОR 2 ) a-1 ) derived from the hydrolyzable organosilane compound of the component (B-1) contained in the component (B) (however, component (C) is not included during step [ii]), and [iii]: A step of adding to the mixture, if there is a remainder in the component (B-1), the remainder thereof, if there is a remainder in the component (B-3), the remainder thereof, and if the component (C) is added, all of it A method for producing a room temperature curable organopolysiloxane composition comprising [2] The method for producing a room temperature curable organopolysiloxane composition according to [1], wherein 10 to 100% by mass of the whole component (B-1) is added in step [i] and 0 to 90% by mass of the whole component (B-1) (100% by mass in total for steps [i] and [iii]) is added in step [iii]. [3] The method for producing a room temperature curable organopolysiloxane composition according to [1] or [2], wherein 10 to 100% by mass of the whole component (B-3) is added in step [i] and 0 to 90% by mass of the whole component (B-3) (100% by mass in total for steps [i] and [iii]) is added in step [iii]. [4] In step [i], 10 to 90% by mass of the total amount of component (B-3) is compounded, and in step [iii], 10 to 90% by mass of the total amount of component (B-3) (100% by mass in total for steps [i] and [iii]) is compounded. The method for producing a room temperature curable organopolysiloxane composition according to any one of [1] to [3]. [5] In step [i], 100% by mass of the total amount of component (B-3) is compounded. The method for producing a room temperature curable organopolysiloxane composition according to any one of [1] to [3]. [6] Furthermore, with respect to 100 parts by mass of component (A), (D) filler: 1 to 1,000 parts by mass, (E) adhesion promoter (excluding component (B-1)): 0.1 to 30 parts by mass, and (F) plasticizer: 1 to 1,000 parts by mass, One or more selected from the above are compounded in any one of steps [i] to [iii]. The method for producing a room temperature curable organopolysiloxane composition according to any one of [1] to [5]. [7] The hydroxylamine compound of component (B-2) is diethylhydroxylamine. The method for producing a room temperature curable organopolysiloxane composition according to any one of [1] to [6]. [8] The organic divalent tin compound of component (B-3) is tin(II) 2-ethylhexanoate. The method for producing a room temperature curable organopolysiloxane composition according to any one of [1] to [7]. [9] The organic tetravalent tin compound of component (B-3) is dioctyltin(IV) dilaurate and / or dioctyltin(IV) dineodecanoate. The method for producing a room temperature curable organopolysiloxane composition according to any one of [1] to [8].

[10] The production method of the room temperature curable organopolysiloxane composition according to any one of [1] to [9], wherein the component (A) is a diorganopolysiloxane having both ends of the molecular chain blocked with silanol groups represented by the following general formula (2) and / or a diorganopolysiloxane having one end of the molecular chain blocked with a silanol group represented by the following general formula (3).

Chemical formula

Chemical formula

[11] the following general formula (1) R 1 4-a Si(OR 2 ) a (1) (In the formula, R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 2 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a is 3 or 4.) a hydrolyzable organosilane compound represented by and / or its partial hydrolyzate: 100 parts by mass, a hydroxylamine compound: 0.1 to 50 parts by mass, and an organic divalent tin compound, or an organic divalent tin compound and an organic tetravalent tin compound: 0.01 to 20 parts by mass A terminal blocking agent for terminally blocking the terminal silanol groups of an organopolysiloxane in which both ends and / or one end of the molecular chain are blocked with silanol groups, which is used as a base polymer of a room temperature curable organopolysiloxane composition composed of a mixture of

Advantages of the Invention

[0008] The manufacturing method of the room-temperature curable organopolysiloxane composition of the present invention can easily manufacture a room-temperature curable organopolysiloxane composition with excellent storage stability by end-capping during the manufacturing process using an endblocking agent composed of a hydrolyzable organosilane compound and / or its partial hydrolyzate, a hydroxylamine compound, and an organic divalent tin compound and / or an organic tetravalent tin compound, starting from an organopolysiloxane having a silanol group at the end as the main agent (base polymer).

Embodiments for Carrying Out the Invention

[0009] Hereinafter, the manufacturing method of the room-temperature curable organopolysiloxane composition of the present invention and the room-temperature curable organopolysiloxane composition will be described in more detail.

[0010] The manufacturing method of the room-temperature curable organopolysiloxane composition of the present invention is (A) Organopolysiloxane having both ends and / or one end of the molecular chain blocked with a silanol group: 100 parts by mass, (B-1) The following general formula (1) R 1 4-a Si(ОR 2 ) a (1) (In the formula, R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, R 2 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a is 3 or 4.) The hydrolyzable organosilane compound and / or its partial hydrolyzate represented by: 0.01 to 30 parts by mass, (B-2) Hydroxylamine compound: 0.01 to 10 parts by mass, (B-3) Organic divalent tin compound and / or organic tetravalent tin compound: 0.001 to 20 parts by mass, and (C) Curing catalyst (excluding components (B-2) and (B-3)): 0 to 20 parts by mass is a manufacturing method of a room-temperature curable organopolysiloxane composition containing [i]: A step of preparing a terminal blocking agent (B) by uniformly mixing in advance a part or all of the component (B-1), all of the component (B-2), and a part or all of the component (B-3) (however, components (A) and (C) are not included during step [i]). [ii]: A step of uniformly mixing the component (A) and the component (B) obtained in step [i] to block the silanol groups at the molecular chain ends of the organopolysiloxane of the component (A) with hydrolyzable organosilyl groups (-SiR 1 4-a (ОR 2 ) a-1 ) derived from the hydrolyzable organosilane compound of the component (B-1) contained in the component (B) to prepare a mixture containing the organopolysiloxane blocked thereby (however, component (C) is not included during step [ii]), and [iii]: A step of blending, with the mixture, the remainder of the component (B-1) if any, the remainder of the component (B-3) if any, and all of the component (C) if blended. It is characterized by including the above.

[0011] [Room temperature curable organopolysiloxane composition] The room temperature curable organopolysiloxane composition obtained by the production method of the present invention contains the following reaction mixture (I), and optionally components (B-1), (B-3), (C), (D) to (F). (I) An organopolysiloxane blocked at both ends and / or one end of the molecular chain with silanol groups, and (B) (B-1) The following general formula (1) R 1 4-a Si(ОR 2 ) a (1) (In the formula, R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, R 2 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a is 3 or 4.) The hydrolyzable organosilane compound represented thereby and / or its partial hydrolyzate, (B-2) A hydroxylamine compound, and (B-3) A terminal blocker composed of a preliminary mixture of an organic divalent tin compound and / or an organic tetravalent tin compound and consists of a hydrolyzable organosilyl group (-SiR 1 4-a (ОR 2 ) a-1 )-blocked organopolysiloxane, a reaction mixture containing (B-1) The hydrolyzable organosilane compound represented by the above general formula (1) and / or its partial hydrolyzate, (B-3) An organic divalent tin compound and / or an organic tetravalent tin compound, (C) A curing catalyst (excluding components (B-2) and (B-3)), (D) A filler, (E) An adhesion promoter (excluding component (B-1)), (F) A plasticizer.

[0012] (A) component: The (A) component used in the room temperature curable organopolysiloxane composition according to the present invention is an organopolysiloxane (i.e., a basically linear polymer having a main chain of a repeating unit of a diorganosiloxane unit with both ends of the molecular chain blocked by silanol groups or one end of the molecular chain blocked by a silanol group and the other end blocked by a trialkylsilyl group) in which both ends and / or one end of the molecular chain are blocked by silanol groups (hydroxyl groups bonded to silicon atoms), and is the starting material of the main agent (base polymer) of the room temperature curable organopolysiloxane composition according to the present invention.

[0013] Specific examples of the (A) component include basically linear diorganopolysiloxanes with both ends of the molecular chain blocked by silanol groups represented by the following general formula (2) and / or basically linear diorganopolysiloxanes with one end of the molecular chain blocked by a silanol group represented by the following general formula (3). [Chemical formula] (In formula (2), R 3 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, A is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, and m is an integer such that the viscosity of this diorganopolysiloxane at 23°C is 100 to 1,000,000 mPa·s.) [Chemical formula] (In formula (3), R 3 , A is the same as in formula (2), and n is an integer such that the viscosity of this diorganopolysiloxane at 23°C is 100 to 1,000,000 mPa·s.)

[0014] Here, in the general formulas (2) and (3), the unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, represented by R 3 include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group; alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group; aryl groups such as phenyl group, tolyl group, xylyl group, α-, β-naphthyl group; aralkyl groups such as benzyl group, 2-phenylethyl group, 3-phenylpropyl group; and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as F, Cl, Br or cyano group, for example, 3-chloropropyl group, 3,3,3-trifluoropropyl group, 2-cyanoethyl group, etc. Among these, it is preferably those excluding aliphatic unsaturated hydrocarbon groups such as alkenyl groups, more preferably alkyl groups such as methyl group, ethyl group and aryl groups such as phenyl group, and particularly preferably methyl group.)

[0015] In the general formulas (2) and (3), A is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, preferably 2 to 4 carbon atoms. Examples of the divalent hydrocarbon group include - (CH 2 ) p - or - (CH = CH) q - (where p represents an integer of 1 to 8, preferably an integer of 1 to 4, and q represents an integer of 1 to 4). Alkylene groups and alkenylene groups such as these are preferred. Among these, an oxygen atom, - CH 2 CH 2 -, - CH 2 CH 2 CH 2 - and - CH = CH - are preferred.

[0016] In the general formulas (2) and (3), m and n are each an integer such that the viscosity of this diorganopolysiloxane at 23 °C is 100 to 1,000,000 mPa·s. Usually, m and n are integers of 20 to 2,000, preferably integers of 20 to 1,600, more preferably integers of 20 to 1,000, and even more preferably integers of about 20 to 500. Here, the viscosity of the diorganopolysiloxane at 23 °C is preferably 100 to 1,000,000 mPa·s, more preferably 300 to 500,000 mPa·s, particularly preferably 500 to 200,000 mPa·s, and especially preferably 1,000 to 100,000 mPa·s. The viscosity is a value measured by a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, etc.) (the same applies hereinafter). Also, the values of m and n indicating the number of repetitions (or degree of polymerization) of the disiloxane units ((R 3 ) 2 SiO 2 / 2 ) constituting the main chain in the organopolysiloxane can usually be determined as the number average degree of polymerization (or number average molecular weight) in terms of polystyrene in gel permeation chromatography (GPC) analysis using toluene or the like as the developing solvent.

[0017] Specific examples of the component (A) include, for example, the following.

Chemical formula

[0018] The organopolysiloxane in which both ends and / or one end of the molecular chain of component (A) are blocked with silanol groups can be used alone or in combination of two or more having different structures and degrees of polymerization.

[0019] (B) component: Component (B), which is a terminal blocking agent used in the room temperature curable organopolysiloxane composition according to the present invention, (B-1) A hydrolyzable organosilane compound represented by the following general formula (1) and / or its partial hydrolyzate R 1 4-a Si(ОR 2 ) a (1) (In the formula, R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, R 2 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a is 3 or 4.), (B-2) A hydroxylamine compound, and (B-3) An organic divalent tin compound and / or an organic tetravalent tin compound comprises, and when compounded in the room temperature curable organopolysiloxane composition, it is prepared as a preliminary mixture in which part or all of component (B-1), all of component (B-2) and part or all of component (B-3) are uniformly mixed in advance, and by being compounded in the room temperature curable organopolysiloxane composition in the form of the homogeneous mixture, it functions as a highly active terminal blocking agent.

[0020] (B-1) component: The hydrolyzable organosilane compound represented by the following general formula (1) and / or its partial hydrolyzate, which is a component (B-1), acts as a crosslinking agent (hardening agent) that terminates the terminal silanol groups of the organopolysiloxane with hydrolyzable silyl groups by a condensation reaction with the organopolysiloxane of component (A) and also forms a crosslinked structure. R 1 4-a Si(ОR 2 ) a (1) (In the formula, R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and each R 2 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a is 3 or 4.)

[0021] Here, in the general formula (1), examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, represented by R 1 include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group; alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group; aryl groups such as phenyl group, tolyl group, xylyl group, α-, β-naphthyl group; aralkyl groups such as benzyl group, 2-phenylethyl group, 3-phenylpropyl group; and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as F, Cl, Br, cyano group, methoxy group, etc., for example, 3-chloropropyl group, 3,3,3-trifluoropropyl group, 2-cyanoethyl group, methoxymethyl group, etc. Among these, alkyl groups such as methyl group, ethyl group, alkenyl groups such as vinyl group, and methoxymethyl group in which one hydrogen atom of the methyl group is substituted with a methoxy group are preferred, and methyl group, vinyl group, and methoxymethyl group are particularly preferred.

[0022] In the general formula (1), R 2 The unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms represented by is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group and other alkyl groups; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group; aryl groups such as phenyl group, tolyl group, xylyl group, α-, β-naphthyl group; aralkyl groups such as benzyl group, 2-phenylethyl group, 3-phenylpropyl group; also, a group in which some or all of the hydrogen atoms of these groups are substituted with a halogen atom such as F, Cl, Br, a cyano group, a methoxy group, etc., for example, 3-chloropropyl group, 3,3,3-trifluoropropyl group, 2-cyanoethyl group, methoxymethyl group, etc. can be exemplified. Among these, alkyl groups such as methyl group and ethyl group are more preferable, and methyl group is particularly preferable.

[0023] (Component (B-1) includes (organo)silane compounds having three or more, preferably three or four hydrolyzable groups such as alkoxy groups in the molecule and their partial hydrolyzates. Specifically, tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, and their partial hydrolyzates, organotrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, methyltris (methoxyethoxy) silane, vinyltris (methoxyethoxy) silane, methoxymethyltrimethoxysilane, methoxymethyltriethoxysilane, ethoxymethyltrimethoxysilane, ethoxymethyltriethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, and their partial hydrolyzates are included. Particularly, tetramethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, methoxymethyltrimethoxysilane, and their hydrolyzates are preferred, but not limited thereto. These can be used alone or in combination of two or more.)

[0024] (The blending amount of the hydrolyzable organosilane compound and / or its partial hydrolyzate of component (B-1) is 0.01 to 30 parts by mass, preferably 0.5 to 10 parts by mass, based on 100 parts by mass of component (A) above. If the amount of component (B-1) is too small, sufficient rubber physical properties may not be obtained even when the resulting composition is cured. If it is too large, rapid curability may be impaired or it may be economically disadvantageous.)

[0025] (Component (B-2): Examples of the hydroxylamine compound as the component (B-2) include hydroxylamine, dimethylhydroxylamine, diethylhydroxylamine, N-ethyl-N-hydroxy-2-propanamine, N-ethyl-N-hydroxy-1-propanamine, N-hydroxy-N-propyl-1-propanamine, N-hydroxy-N-methyl-2-butanamine, N-hydroxy-N-propyl-1-butanamine, N-ethyl-N-hydroxy-1-butanamine, N-hydroxy-N-methyl-1-butanamine, N-hydroxy-N,2-dimethyl-1-propanamine, N-hydroxy-N-(1-methylethyl)-2-propanamine, N-hydroxy-N-propyl-2-butanamine, N-ethyl-N-hydroxy-2-butanamine, N-hydroxy-N-(1-methylethyl)-1-butanamine, N-benzoyl-N-phenylhydroxylamine, and the like. Among these, diethylhydroxylamine, which has high safety and is easily available, is preferred.

[0026] The blending amount of the component (B-2) is 0.01 to 10 parts by mass, preferably 0.1 to 1 part by mass, based on 100 parts by mass of the component (A). If the amount of the component (B-2) is too small, the end-capping reaction of the terminal silanol groups of the component (A) does not proceed efficiently. If it is too large, problems such as deterioration of storage stability and economic disadvantage will occur.

[0027] Component (B-3): The component (B-3) is one or more selected from organic divalent tin compounds and organic tetravalent tin compounds. Among the component (B-3), as the organic divalent tin compound, a divalent tin salt of a carboxylic acid (a salt of a carboxylic acid and divalent tin (II)) is preferred, and examples thereof include divalent tin (II) dicarboxylate compounds such as tin (II) 2-ethylhexanoate [also known as: tin (II) octoate], tin (II) octanoate, and tin (II) neodecanoate. Among these, tin (II) 2-ethylhexanoate, which is easily available, is preferred. Among the components of (B-3), examples of the tetravalent organic tin compounds include dialkyltin(IV) diester compounds such as dibutyltin(IV) diacetate, dibutyltin(IV) dilaurate, dibutyltin(IV) dioctoate, dioctyltin(IV) dilaurate, dioctyltin(IV) dineodecanoate, dibutyltin(IV) diacetoacetate, and dialkyltin(IV) dialkoxy compounds such as di-n-butyl-dimethoxytin(IV). Among these, dialkyltin(IV) diester compounds are preferred, and particularly, dioctyltin(IV) dilaurate and dioctyltin(IV) dineodecanoate, which are easily available, are preferred.

[0028] The blending amount of the component (B-3) is 0.001 to 20 parts by mass, preferably 0.01 to 10 parts by mass, and more preferably 0.02 to 5 parts by mass with respect to 100 parts by mass of the component (A). When the amount of the component (B-3) is within the above range, the end-capping reaction of the room-temperature curable organopolysiloxane composition according to the present invention can proceed efficiently. When it exceeds 20 parts by mass, it becomes disadvantageous in production, such as gel generation during the end-capping process, or economically disadvantageous.

[0029] When the divalent organic tin compound and the tetravalent organic tin compound are used in combination, the blending ratio thereof is preferably in a mass ratio of divalent organic tin compound:tetravalent organic tin compound = 1:50 to 5:1, particularly 1:20 to 2:1, based on the total blending amount in steps [i] and [iii]. When the divalent organic tin compound and the tetravalent organic tin compound are used in combination in step [i], the blending ratio in step [i] is preferably in a mass ratio of divalent organic tin compound:tetravalent organic tin compound = 1:10 to 2:1, particularly 1:5 to 1:1.

[0030] When preparing the end-capping agent as component (B), the compounding ratios of components (B-1), (B-2), and (B-3) are such that, based on 100 parts by mass of component (B-1), component (B-2) is 0.1 to 50 parts by mass, particularly preferably 1 to 10 parts by mass, and component (B-3) is 0.01 to 20 parts by mass, particularly preferably 0.01 to 10 parts by mass. When the compounding ratio of component (B) is within the above range, it is preferable because the end-capping reaction of the organopolysiloxane of component (A) can proceed efficiently. If there is too much of component (B-2) and / or component (B-3), gel may form during the end-capping process or it may be economically disadvantageous. If there is too little of component (B-2) and / or component (B-3), the end-capping reaction of the terminal silanol groups of component (A) may not proceed efficiently.

[0031] The compounding amount of the end-capping agent as component (B) is 0.021 to 50 parts by mass based on 100 parts by mass of component (A) above, preferably 0.3 to 15 parts by mass, and more preferably 0.6 to 12 parts by mass. If there is too little of component (B), the end-capping of component (A) will not proceed sufficiently, and if there is too much, it will be economically disadvantageous.

[0032] Component (C): Component (C) according to the present invention is a curing catalyst (non-metal organic catalyst and / or metal catalyst) that is distinguished from components (B-2) and (B-3) above, and acts to promote the curing of the room-temperature curable organopolysiloxane composition according to the present invention.

[0033] As the non-metallic organic catalyst of the curing catalyst, those known as the curing accelerator of the condensation-curing type organopolysiloxane composition can be used, and there is no particular limitation. For example, phosphazene-containing compounds such as N,N,N’,N’,N'',N''-hexamethyl-N'''-(trimethylsilylmethyl)-phosphorimidic triamide, amine compounds such as hexylamine and dodecylamine phosphate or salts thereof, quaternary ammonium salts such as benzyltriethylammonium acetate, silanes and siloxanes containing a guanidyl group such as tetramethylguanidylpropyltrimethoxysilane, tetramethylguanidylpropylmethyldimethoxysilane, and tetramethylguanidylpropyltris(trimethylsiloxy)silane are exemplified, but the non-metallic organic catalyst is not limited thereto. Further, one kind or two or more kinds of the non-metallic organic catalyst may be used.

[0034] As the metal catalyst of the curing catalyst, those known as the curing accelerator of the condensation-curing type organopolysiloxane composition can be used, and there is no particular limitation. For example, titanates or titanium chelate compounds such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetonato)titanium, titanium isopropoxyoctylene glycol, and titanium diisopropoxybis(ethyl acetoacetate); alcoholate aluminum compounds such as aluminum isopropylate and aluminum secondary butyrate; aluminum chelate compounds such as aluminum alkyl acetate·diisopropylate and aluminum bisethyl acetoacetate·monoacetylacetonate; metal organic compounds such as zinc naphthenate, zinc stearate, zinc-2-ethyloctoate, iron-2-ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, cobalt naphthenate, neodecanoic acid bismuth(III), bismuth(III) 2-ethylhexanoate, bismuth(III) citrate, and bismuth octylate; and lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate, and lithium oxalate are exemplified, but the metal catalyst is not limited thereto. Also, one kind or two or more kinds of the metal catalyst may be used.

[0035] (C) The compounding amount of the curing catalyst is 0 to 20 parts by mass with respect to 100 parts by mass of the above (A) component. When compounding, it is preferably 0.001 to 20 parts by mass, and more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the above (A) component. If the amount of component (C) is too small, sufficient curability may not be obtained. If it is too large, the curability is too fast, resulting in insufficient working time and being economically disadvantageous.

[0036] When a part of the above component (B-3) is distributed and blended in step [i] and the remaining part is distributed and blended in step [iii], in step [iii], the component (C) (i.e., a curing catalyst other than the above components (B-2) and (B-3)) can be blended as an optional component as needed, and can be appropriately blended in the range of 20 parts by mass or less (0 to 20 parts by mass) with respect to 100 parts by mass of the above component (A). On the other hand, when 100% by mass of the component (B-3) is blended in step [i] (i.e., when the component (B-3) is not blended in step [iii]), when the component (B-3) contains an organic tetravalent tin compound (i.e., when the component (B-3) is only an organic tetravalent tin compound or contains an organic divalent tin compound and an organic tetravalent tin compound), in step [iii], the component (C) (i.e., a curing catalyst other than the above components (B-2) and (B-3)) can be blended as an optional component as needed, and can be appropriately blended in the range of 20 parts by mass or less (0 to 20 parts by mass) with respect to 100 parts by mass of the above component (A). Further, when the component (B-3) is only an organic divalent tin compound, the component (C) is an essential component, and in step [iii], it is preferable to blend 0.001 to 20 parts by mass, preferably 0.01 to 10 parts by mass of the component (C) with respect to 100 parts by mass of the above component (A).

[0037] Component (D): (D) component is a filler (inorganic filler and / or organic resin filler), which is an optional component incorporated into the room-temperature curable organopolysiloxane composition according to the present invention as required, and is used to impart sufficient mechanical strength to the cured product formed from this composition. Known fillers can be used as this filler. As the inorganic filler, for example, reinforcing silica-based fillers such as fine powder silica, fumed silica (fumed silica or dry silica), precipitated silica (wet silica), silica obtained by hydrophobizing the surface of these silicas with an organosilicon compound, glass beads, glass balloons, transparent resin beads, silica aerogel, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, fumed metal oxides and other metal oxides, quartz powder (crystalline silica), carbon black, talc, zeolite, bentonite and other reinforcing agents, asbestos, glass fiber, carbon fiber, colloidal calcium carbonate, calcium carbonate such as heavy calcium carbonate, metal carbonates such as magnesium carbonate and zinc carbonate, glass wool, fine mica powder, fused silica powder, etc. As the organic resin filler, for example, synthetic resin powders such as polystyrene, polyvinyl chloride, and polypropylene are used. Among these fillers, inorganic fillers such as silica, calcium carbonate, and zeolite are preferred, and particularly fumed silica and calcium carbonate with hydrophobized surfaces are preferred.

[0038] When the filler of component (D) is incorporated, its incorporation amount is preferably 1 to 1,000 parts by mass, particularly 5 to 400 parts by mass, based on 100 parts by mass of the above component (A). Incorporating it rather than not incorporating it tends to make the cured product obtained from this composition exhibit sufficient mechanical strength. Also, when used in an amount more than 1,000 parts by mass, not only does the viscosity of the composition increase and the workability deteriorate, but also the rubber strength after curing tends to decrease and it becomes difficult to obtain rubber elasticity.

[0039] (E) component: (E) component is an adhesion promoter (excluding the (B-1) component), and is an optional component that is blended into the room-temperature curable organopolysiloxane composition according to the present invention as needed, and is used to impart sufficient adhesiveness to the cured product formed from this composition. Specifically, aminosilanes such as γ-aminopropyltriethoxysilane, 3-2-(aminoethylamino)propyltrimethoxysilane [alias: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane], epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, (meth)acrylic silanes such as γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, isocyanate silanes such as γ-isocyanatopropyltrimethoxysilane, etc., and hydrolyzable organosilane compounds having a monovalent hydrocarbon group containing a functional group having a heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom (excluding a guanidyl group) other than a hydrolyzable group (so-called carbon-functional silane or silane coupling agent), etc. are preferably blended. Note that the adhesion promoter ((E) component) (carbon-functional silane or silane coupling agent) is clearly distinguished from the hydrolyzable organosilane compound and / or its partial hydrolyzate of the above (B-1) component in that it has a monovalent hydrocarbon group containing a functional group having a heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom (excluding a guanidyl group) other than a hydrolyzable group in the molecule (however, it does not contain an organooxy-substituted alkyl group such as a methoxymethyl group).

[0040] When blending the adhesion promoter of the (E) component, the blending amount is preferably 0.1 to 30 parts by mass, particularly 0.5 to 20 parts by mass, based on 100 parts by mass of the above (A) component. If it exceeds 30 parts by mass, the curability may become insufficient or it may be economically disadvantageous. The (E) component is preferably not blended during the following steps [i] and [ii], and is blended during step [iii] as needed.

[0041] (F) component: (F) The component is a plasticizer and is an optional component that is blended into the room temperature curable organopolysiloxane composition according to the present invention as needed. Without impairing the mechanical properties and flame retardancy of the cured product formed from this composition, it can be adjusted to a viscosity that is easy to handle during construction.

[0042] Examples of the plasticizer used in the room temperature curable organopolysiloxane composition according to the present invention include dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), diheptyl phthalate (DHP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), ditridecyl phthalate (DTDP), butyl benzyl phthalate (BBP), dicyclohexyl phthalate (DCHP), tetrahydrophthalic acid ester, dioctyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-n-alkyl adipate, dibutyl diglycol adipate (BXA), bis(2-ethylhexyl) azelate (DOZ), dibutyl sebacate (DBS), dioctyl sebacate (DOS), dibutyl maleate (DBM), di-2-ethylhexyl maleate (DOM), dibutyl fumarate (DBF), tricresyl phosphate (TCP), triethyl phosphate (TEP), tributyl phosphate (TBP), tris(2-ethylhexyl) phosphate (TOP), tris(chloroethyl) phosphate (TCEP), tris(dichloropropyl) phosphate (CPP), tributoxyethyl phosphate (TBXP), tris(β-chloropropyl) phosphate (TMCPP), triphenyl phosphate (TPP), octyldiphenyl phosphate (ODP), acetyltriethyl citrate, tributyl acetyl citrate, etc. In addition, there are trimellitic acid-based plasticizers, polyester-based plasticizers, chlorinated paraffins, stearic acid-based plasticizers, etc. Furthermore, silicone oils (non-functional organopolysiloxanes) such as dimethylpolysiloxane, and recently, petroleum-based high-boiling solvents such as polyoxypropylene glycol-based, paraffin-based, naphthene-based, and isoparaffin-based solvents can be mentioned. These can be used alone or in combination of two or more. Among them, silicone oil is particularly preferred.

[0043] As the above silicone oil (non-functional organopolysiloxane), preferably, an organopolysiloxane represented by the following general formula (4) can be used.

Chemical formula

[0044] In the above formula (4), R 4 is a monovalent hydrocarbon group having 1 to 20 carbon atoms that is independently unsubstituted or substituted and does not contain an aliphatic unsaturated bond. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group, and those in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as F, Cl, Br, for example, chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group, etc. can be mentioned.)

[0045] In addition, in the organopolysiloxane represented by the above formula (4), the value of b indicating the repeating number (degree of polymerization) of the diorganosiloxane unit is usually an integer of about 3 to 3,000, preferably 5 to 2,000, more preferably 10 to 1,000.) Here, the viscosity of the organopolysiloxane at 23 °C is preferably 1.5 to 1,000,000 mPa·s, more preferably 10 to 100,000 mPa·s.)

[0046] When compounding the (F) component, the compounding amount is preferably 1 to 1,000 parts by mass, more preferably 2 to 500 parts by mass, and still more preferably 5 to 200 parts by mass with respect to 100 parts by mass of the above (A) component. When the amount of the (F) component is within the above range, it is preferable because the mechanical properties and flame retardancy of the room temperature curable organopolysiloxane composition according to the present invention can be adjusted to a viscosity that is easy to handle in construction without impairing them.

[0047] [Other components] In addition, in the room temperature curable organopolysiloxane composition according to the present invention, a thixotropic agent can be compounded as an optional additive within a range that does not impair the object of the present invention. Examples of the thixotropic agent include polyether compounds typified by polyethylene oxide (polyoxyethylene), polypropylene oxide (polyoxypropylene), ethylene oxide·propylene oxide copolymer (polyoxyethylene·polyoxypropylene copolymer), and polymers in which the molecular chain terminals (one terminal or both terminals) of these are blocked with alkyl ethers, and compounds obtained by subjecting such polyether compounds to silane modification or silicone modification, polyether phosphate esters, polyether fatty acid esters, fatty acid amide waxes, hydrogenated castor oil, oxidized polyolefins, and the like.

[0048] In addition, in the room-temperature curable organopolysiloxane composition according to the present invention, as optional additives, glycerin esters of fatty acids having fatty acid ester groups such as triacetin, diacetin, monoacetin, tributyrin, tricaprylin, tristearin, glycerol diacetate laurate, trimethylolpropane tristearate, trimethylolpropane triacetate, pentaerythritol monoacetate, etc., fatty acid ester compounds of polyhydric alcohols having three or more fatty acid ester groups or a total of three or more fatty acid ester groups and hydroxyl groups in the molecule can be blended as storage stabilizers (preservation improvers). In addition, known additives such as pigments, dyes, anti-aging agents, antioxidants, antistatic agents, flame retardants such as antimony oxide and chlorinated paraffin can be blended within a range that does not impair the object of the present invention. Furthermore, a fungicide and an antibacterial agent can also be blended.

[0049] Furthermore, the room-temperature curable organopolysiloxane composition according to the present invention may use an organic solvent as needed. Examples of the organic solvent include aliphatic hydrocarbon compounds such as n-hexane, n-heptane, isooctane, and isododecane, aromatic hydrocarbon compounds such as toluene and xylene, chain siloxanes such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and 2-(trimethylsiloxy)-1,1,1,2,3,3,3-heptamethyltrisiloxane, and cyclic siloxanes such as octamethylcyclopentasiloxane and decamethylcyclopentasiloxane. The amount of the organic solvent may be appropriately adjusted within a range that does not prevent the effects of the present invention.

[0050] [Method for Producing Room-Temperature Curable Organopolysiloxane Composition] The method for producing a room-temperature curable organopolysiloxane composition of the present invention is as follows for each of the above-described components. A step (step [i]) of preparing a terminal blocking agent (B) by uniformly mixing at least a part or all of the (B-1) component, all of the (B-2) component, and a part or all of the (B-3) component, excluding the (A) and (C) components; a step of uniformly mixing at least all of the (A) component, excluding the (C) component, and all of the (B) component, which is the terminal blocking agent obtained in step [i], and blocking the silanol groups at the molecular chain ends of the organopolysiloxane of the (A) component with hydrolyzable organosilyl groups (-SiR 1 4-a (ОR 2 ) a-1 ) derived from the hydrolyzable organosilane compound of the (B-1) component contained in the (B) component to prepare a mixture containing an organopolysiloxane (terminal blocking step) (step [ii]); and a step (step [iii]) of adding, to the mixture, the remainder of the (B-1) component if any, the remainder of the (B-3) component if any, and all of the (C) component if the (C) component is to be blended.

[0051] In the method for producing a room-temperature curable organopolysiloxane composition of the present invention, the hydrolyzable organosilane compound and / or its partial hydrolyzate of the (B-1) component, with respect to the above steps [i] and [iii], 10 to 100% by mass, particularly 30 to 100% by mass, and more preferably 50 to 100% by mass of the whole (B-1) component is blended in step [i], and 0 to 90% by mass, particularly 0 to 70% by mass, and more preferably 0 to 50% by mass of the whole (B-1) component is blended in step [iii]. If the blending ratio of the (B-1) component in step [i] is too small, the terminal blocking reaction does not proceed sufficiently, and when the (C) component or (E) component is added in step [iii] after the terminal blocking step, gelation or thickening may occur, which is disadvantageous in production.

[0052] Also, in the method for producing the room-temperature curable organopolysiloxane composition of the present invention, regarding the above steps [i] and [iii], when the component (B-3) is only an organic divalent tin compound, it is preferable to blend 100% by mass of the entire component (B-3) (that is, all of the organic divalent tin compound) in the above step [i]. However, when the component (B-3) contains an organic tetravalent tin compound (that is, when the component (B-3) is only an organic tetravalent tin compound, or when it contains both an organic divalent tin compound and an organic tetravalent tin compound), 10 to 100% by mass, particularly 30 to 100% by mass, and more preferably 50 to 100% by mass of the entire component (B-3) (particularly, the entire organic tetravalent tin compound) is blended in step [i], and 0 to 90% by mass, particularly 0 to 70% by mass, and more preferably 0 to 50% by mass of the entire component (B-3) (particularly, the entire organic tetravalent tin compound) is blended in step [iii] (the total of steps [i] and [iii] is 100% by mass). If the blending ratio of the component (B-3) in step [i] is too small, the end-capping reaction does not proceed sufficiently, and when the component (C) or component (E) is added in step [iii] after the end-capping step, gelation or thickening may occur, which is disadvantageous in production. Furthermore, regarding the above steps [i] and [iii], when a part of the component (B-3) (particularly, the organic tetravalent tin compound) is distributed and blended in step [i] and the remainder is blended in step [iii], 10 to 90% by mass, particularly 20 to 60% by mass of the entire component (B-3) (particularly, the entire organic tetravalent tin compound) is blended in step [i], and 90 to 10% by mass, particularly 80 to 40% by mass of the entire component (B-3) (particularly, the entire organic tetravalent tin compound) is blended in step [iii] (the total of steps [i] and [iii] is 100% by mass).

[0053] In addition, when a part of the component (B-3) (particularly, the organic tetravalent tin compound) is distributed and blended in step [i] and the remainder is blended in step [iii], in step [iii], the component (C) (that is, a curing catalyst other than the components (B-2) and (B-3)) can be appropriately blended as an optional component in the range of 20 parts by mass or less (0 to 20 parts by mass) with respect to 100 parts by mass of the above component (A) as needed. On the one hand, when the component (B-3) is blended at 100% by mass in step [i] (i.e., when the component (B-3) is not blended in step [iii]), if the component (B-3) contains an organic tetravalent tin compound (i.e., when the component (B-3) is only an organic tetravalent tin compound or contains both an organic divalent tin compound and an organic tetravalent tin compound), in step [iii], the component (C) (i.e., the curing catalyst other than the above-mentioned components (B-2) and (B-3)) can be blended as an optional component as needed, and can be appropriately blended in the range of 20 parts by mass or less (0 to 20 parts by mass) with respect to 100 parts by mass of the component (A). Also, when the component (B-3) is only an organic divalent tin compound, the component (C) is an essential component, and in step [iii], it is preferable to blend the component (C) in the range of 0.001 to 20 parts by mass, preferably 0.01 to 10 parts by mass, with respect to 100 parts by mass of the component (A).

[0054] In step [i], each component constituting the end-capping agent only needs to form a homogeneous mixture, and as the mixing conditions, any mixing method can be used, such as a method of mixing using a mixing stirrer, a method of charging into a sealed container and mixing with a shaker, or a method of mixing with a stirrer in a predetermined container.

[0055] By step [i], an end-capping agent (B) is obtained, which contains at least a part or all of the component (B-1), all of the component (B-2), and a part or all of the component (B-3), excluding the components (A) and (C), and these are uniformly mixed.

[0056] In step [ii], the mixing of each component can be carried out under substantially anhydrous conditions, at normal pressure or reduced pressure, under any temperature conditions (usually 0 to 100 °C, preferably 10 to 70 °C), and the time is usually 1 minute to 5 hours, preferably about 5 minutes to 2 hours.

[0057] By step [ii], at least the component (A) and the component (B) are included, excluding the component (C), and the silanol group at the molecular chain end of the organopolysiloxane of the component (A) is a hydrolyzable organosilyl group (-SiR) derived from the hydrolyzable organosilane compound of the component (B-1) contained in the component (B).1 4-a (OR 2 ) a-1 A reaction mixture (I) containing an organopolysiloxane blocked with ()) is obtained.

[0058] After the terminal blocking step (step [ii]), if there is a remainder in the component (B-1), the remainder thereof, if there is a remainder in the component (B-3), the remainder thereof, and if the component (C) is blended, all of it are blended (step [iii]). Here, the component (D), the component (E), the component (F) and other components may be mixed in step [iii], or may be mixed simultaneously during the terminal blocking step (step [ii]), or may even be mixed during the preparation of the terminal blocking agent (step [i]). However, since gelation or thickening may occur when the component (C) is mixed during the terminal blocking step (step [ii]), it is added in step [iii] which is after the terminal blocking step. Also, when the component (E) is an aminosilane, if it is mixed during the step of terminal blocking, the properties of the mixture may become saggy, which may be disadvantageous especially when used as an adhesive or a construction sealant. Therefore, it is preferably added in step [iii] which is after the terminal blocking step.

[0059] In step [iii], the mixing of each component may be carried out under substantially anhydrous conditions, at normal pressure or reduced pressure, under any temperature conditions (usually 0 to 100 °C, preferably 10 to 70 °C), and the time is usually 1 minute to 5 hours, preferably about 5 minutes to 2 hours.

[0060] In the terminal-blocking step (Step [ii]), if the terminal blocking of component (A) is insufficient, gelation or thickening may occur when component (C) or component (E) is added during Step [iii] after the terminal-blocking step. However, the room-temperature curable organopolysiloxane composition produced under the above-described conditions can be produced from an organopolysiloxane having an inexpensive terminal functional group of a silanol group as a starting material under mild conditions and in a very short time, resulting in improved productivity. Also, since the storage stability is good, it is economically advantageous because the terminal-blocking step proceeds well.

[0061] The room-temperature curable organopolysiloxane composition obtained by the production method of the present invention cures by being left at room temperature (23°C ± 15°C). For its molding method, curing conditions, etc., known methods and conditions corresponding to the type of the composition can be employed. In particular, the one-component type composition is stored in the absence of moisture, i.e., in a sealed container blocking moisture, and cured easily at room temperature (23°C ± 15°C) by being exposed to moisture in the air during use.

[0062] Further, the obtained cured product exhibits good flexibility and has rubber elasticity, and thus is useful as a coating agent, an adhesive, a sealing material (for example, a building sealant, etc.). The method of using the room-temperature curable organopolysiloxane composition obtained by the production method of the present invention as a coating agent, an adhesive, or a sealing material may follow a conventionally known method of use and is not particularly limited.

[0063] Examples of the article having a coating layer composed of the cured product of the room-temperature curable organopolysiloxane composition obtained by the production method of the present invention include articles made of, for example, glasses, various resins, various metals, etc., but the material and shape of the base material are not particularly limited.

[0064] Examples of articles that are adhered and / or sealed with a cured product of the room-temperature curable organopolysiloxane composition obtained by the production method of the present invention include, for example, articles made of various glasses, various metals, etc., but the material and shape of the base material are not particularly limited.

Examples

[0065] Hereinafter, examples , Reference Example and comparative examples will be shown to specifically explain the present invention, but the present invention is not limited to the following examples. In the following specific examples, "parts" means "parts by mass", and the viscosity is the measured value by a rotational viscometer at 23°C. Also, the preparation of the composition was carried out at an indoor temperature of 23°C.

[0066] [Example 1] 100 parts of vinyltrimethoxysilane, 4 parts of diethylhydroxylamine, and 0.4 part of tin(II) 2-ethylhexanoate were uniformly mixed in advance to prepare a terminal blocking agent 1 (step [i]). To 100 parts of a linear dimethylpolysiloxane with silanol groups blocking both ends of the molecular chain and a viscosity of 50,000 mPa·s, 10.44 parts of the terminal blocking agent 1 prepared above was added and mixed under moisture shielding for 30 minutes to perform a terminal blocking step of blocking the silanol groups at both ends of the molecular chain of the linear dimethylpolysiloxane with vinyldimethoxysilyl groups (step [ii]). Next, 40 parts of a linear dimethylpolysiloxane with trimethylsilyl groups blocking both ends of the molecular chain and a viscosity of 100 mPa·s, and 15 parts of fumed silica were added to the mixture, and the mixture was mixed under reduced pressure for 30 minutes. Then, 0.8 part of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and 0.3 part of dioctyltin(IV) dineodecanoate (Neostan U-830, manufactured by Nitto Kasei Co., Ltd.) were added to the mixture, and the mixture was mixed under reduced pressure for 15 minutes until uniform to prepare Composition 1 (step [iii]).

[0067] [Example 2] 100 parts of linear dimethylpolysiloxane with both ends of the molecular chain blocked by silanol groups and a viscosity of 50,000 mPa·s, 40 parts of linear dimethylpolysiloxane with both ends of the molecular chain blocked by trimethylsilyl groups and a viscosity of 100 mPa·s, 15 parts of fumed silica, and 0.5 part of polyoxyethylene polyoxypropylene monobutyl ether (Uni Lub C, manufactured by NOF Corporation) were mixed under reduced pressure for 30 minutes. Subsequently, 10.44 parts of the end-capping agent 1 prepared in the same manner as in Example 1 was added, and the mixture was mixed under reduced pressure for 30 minutes to perform an end-capping step of blocking the silanol groups at both ends of the molecular chain of the linear dimethylpolysiloxane with vinyldimethoxysilyl groups (Step [ii]). After mixing under reduced pressure, 0.8 part of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and 0.3 part of dioctyltin(IV) dineodecanoate (Neo-Stann U-830, manufactured by Nitto Kasei Co., Ltd.) were added to the mixture, and the mixture was mixed under reduced pressure until homogeneous for 15 minutes to prepare Composition 2 (Step [iii]).

[0068] Reference Example In Step [i], instead of 0.4 part of tin(II) 2-ethylhexanoate, 2 parts of dioctyltin(IV) dineodecanoate was used to prepare an end-capping agent 2. An end-capping step (Step [ii]) was performed by adding 10.6 parts of the end-capping agent 2, and Composition 3 was prepared in the same manner as in Example 2 except that 0.3 part of dioctyltin(IV) dineodecanoate was not added in Step [iii].

[0069] [Example 3 In Step [i], instead of 0.4 part of tin(II) 2-ethylhexanoate, 0.2 part of tin(II) 2-ethylhexanoate and 1 part of dioctyltin(IV) dineodecanoate were used to prepare an end-capping agent 3. An end-capping step (Step [ii]) was performed by adding 10.12 parts of the end-capping agent 3, and Composition 4 was prepared in the same manner as in Example 2.

[0070] [Example 4 ​​​​100 parts of methyltrimethoxysilane, 4 parts of diethylhydroxylamine, and 0.4 part of tin(II) 2-ethylhexanoate were uniformly mixed in advance to prepare a terminal blocking agent 4 (step [i]). In Example 2, instead of 100 parts of a linear dimethylpolysiloxane with both molecular chain ends blocked with silanol groups and a viscosity of 50,000 mPa·s, 85 parts of a linear dimethylpolysiloxane with both molecular chain ends blocked with silanol groups and a viscosity of 20,000 mPa·s and 50 parts of a linear dimethylpolysiloxane with one molecular chain end blocked with a silanol group and the other molecular chain end blocked with a trimethylsilyl group and a viscosity of 20,000 mPa·s were used. Instead of 40 parts of a linear dimethylpolysiloxane with both molecular chain ends blocked with trimethylsilyl groups and a viscosity of 100 mPa·s, 5 parts of a linear dimethylpolysiloxane with both molecular chain ends blocked with trimethylsilyl groups and a viscosity of 20,000 mPa·s were used. Instead of 10.44 parts of terminal blocking agent 1, 10.44 parts of terminal blocking agent 4 were used. A terminal blocking step (step [ii]) was performed to block the silanol groups at both molecular chain ends and the silanol group at one molecular chain end of the linear dimethylpolysiloxane with vinyldimethoxysilyl groups in the same manner as in Example 2, except for this, to prepare Composition 5.

[0071] [Example 5 A terminal blocking step was performed to block the silanol groups at both molecular chain ends of the linear dimethylpolysiloxane with vinyldimethoxysilyl groups by mixing 100 parts of a linear dimethylpolysiloxane with both molecular chain ends blocked with silanol groups and a viscosity of 20,000 mPa·s, 40 parts of a linear dimethylpolysiloxane with both molecular chain ends blocked with trimethylsilyl groups and a viscosity of 100 mPa·s, and 5.22 parts of terminal blocking agent 1 prepared in the same manner as in Example uniformly for 30 minutes under moisture shielding (step [ii]). ​Next, 100 parts of colloidal calcium carbonate and 100 parts of heavy calcium carbonate were mixed with the mixture under reduced pressure for 30 minutes. After mixing under reduced pressure, 5 parts of methyltrimethoxysilane, 0.5 part of aminopropyltriethoxysilane, 1 part of triacetin, and 5 parts of titanium diisopropoxybis(ethylacetoacetate) (Organix TC-750, manufactured by Matsumoto Fine Chemical Co., Ltd.) were added to the mixture, and the mixture was mixed under reduced pressure until homogeneous for 15 minutes to prepare Composition 6 (Step [iii]).

[0072] [Comparative Example 1] In Example 1, an attempt was made to prepare Composition 7 in the same manner as in Example 1, except that 10 parts of vinyltrimethoxysilane was used instead of 10.44 parts of End-capping Agent 1. However, after adding aminosilane (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane) and tin catalyst (dioctyltin(IV) dineodecanoate) in Step [iii], the system gelled and Composition 7 could not be prepared.

[0073] [Comparative Example 2] In Example 2, an attempt was made to prepare Composition 8 in the same manner as in Example 2, except that 10 parts of vinyltrimethoxysilane and 1 part of the basic silane compound represented by the following Structural Formula (5) were used instead of 10.44 parts of End-capping Agent 1. However, after adding aminosilane (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane) and tin catalyst (dioctyltin(IV) dineodecanoate) in Step [iii], the system gelled and Composition 8 could not be prepared.

Chemical Formula

[0074] [Comparative Example 3] Example 5 Composition 9 was prepared in the same manner as in Example 5 except that 5.22 parts of End-capping Agent 1 was not added.

[0075] [Evaluation Test] Examples 1 to 5, Reference Example The tack-free times of the compositions immediately after preparation prepared in Examples 1 to and Comparative Example 3 were measured. 5, Reference Example In addition, each composition immediately after preparation prepared in Examples 1 to

[0076] [Storage Stability] Each composition prepared in Examples 1 to 5, Reference Example and Comparative Example 3 was put into a polyethylene sealing material cartridge (capacity 330 mL), and the inner plug was inserted and sealed. After storing this cartridge in a dryer at 70°C for 7 days, it was taken out, and the tack-free time was measured in the same manner as above. If the time was within 2 times the tack-free time of each composition immediately after preparation, it was marked as ○ (qualified), and if it took a longer time than 2 times, it was marked as × (unqualified). The above results are shown in Table 1.

[0077]

Table 1

[0078] From the results in Table 1, it was revealed that Examples 1 to 5, Reference Example were easier to prepare the cured composition and had better storage stability compared to the corresponding Comparative Examples 1 to 3.

[0079] Note that the present invention is not limited to the above embodiments. The above embodiments are examples, and any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same operational effects is included in the technical scope of the present invention.

Claims

1. (A) Organopolysiloxane in which both ends and / or one end of the molecular chain are blocked with silanol groups: 100 parts by mass, (B-1) The following general formula (1) R 1 4-a Si(OR 2 ) a (1) (In the formula, R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 2 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a is 3 or 4.) Hydrolyzable organosilane compound represented by and / or its partial hydrolyzate: 0.01 to 30 parts by mass, (B-2) Hydroxylamine compound: 0.01 to 10 parts by mass, (B-3) Organic divalent tin compound, or organic divalent tin compound and organic tetravalent tin compound: 0.001 to 20 parts by mass, and (C) Curing catalyst (excluding components (B-2) and (B-3)): 0 to 20 parts by mass A method for producing a room-temperature curable organopolysiloxane composition containing [i]: A step of uniformly mixing a part or all of the component (B-1), all of the component (B-2), and a part or all of the component (B-3) to prepare a terminal blocking agent (B) (however, components (A) and (C) are not included during step [i]), [ii]: A step of uniformly mixing the component (A) and the component (B) obtained in step [i] to block the silanol groups at the molecular chain ends of the organopolysiloxane of the component (A) with hydrolyzable organosilyl groups (—SiR 1 4-a (OR 2 ) a-1 ) derived from the hydrolyzable organosilane compound of the component (B-1) contained in the component (B) to prepare a mixture containing an organopolysiloxane (however, the component (C) is not contained during step [ii]), and [iii]: A step of adding to the mixture, if there is a remainder in the component (B-1), the remainder thereof, if there is a remainder in the component (B-3), the remainder thereof, and if the component (C) is added, all of it A method for producing a room-temperature curable organopolysiloxane composition including

2. The method for producing a room-temperature curable organopolysiloxane composition according to claim 1, wherein 10 to 100% by mass of the entire component (B-1) is added in step [i], and 0 to 90% by mass of the entire component (B-1) (100% by mass in total of steps [i] and [iii]) is added in step [iii].

3. The method for producing a room-temperature curable organopolysiloxane composition according to claim 1 or 2, wherein 10 to 100% by mass of the entire component (B-3) is added in step [i], and 0 to 90% by mass of the entire component (B-3) (100% by mass in total of steps [i] and [iii]) is added in step [iii].

4. The method for producing a room-temperature curable organopolysiloxane composition according to any one of claims 1 to 3, wherein 10 to 90% by mass of the entire component (B-3) is added in step [i], and 10 to 90% by mass of the entire component (B-3) (100% by mass in total of steps [i] and [iii]) is added in step [iii].

5. The method for producing a room-temperature curable organopolysiloxane composition according to any one of claims 1 to 3, wherein 100% by mass of the entire component (B-3) is added in step [i].

6. Furthermore, based on 100 parts by mass of component (A), (D) Filler: 1 to 1,000 parts by mass, (E) Adhesion promoter (excluding component (B-1)): 0.1 to 30 parts by mass, and (F) Plasticizer: 1 to 1,000 parts by mass, The method for producing a room-temperature curable organopolysiloxane composition according to any one of claims 1 to 5, wherein one or more selected from the above are blended in any one of steps [i] to [iii].

7. The method for producing a room-temperature curable organopolysiloxane composition according to any one of claims 1 to 6, wherein the hydroxylamine compound of component (B-2) is diethylhydroxylamine.

8. The method for producing a room-temperature curable organopolysiloxane composition according to any one of claims 1 to 7, wherein the organic divalent tin compound of component (B-3) is tin(II) 2-ethylhexanoate.

9. The method for producing a room-temperature curable organopolysiloxane composition according to any one of claims 1 to 8, wherein the organic tetravalent tin compound of component (B-3) is dioctyltin(IV) dilaurate and / or dioctyltin(IV) dineodecanoate.

10. The method for producing a room-temperature curable organopolysiloxane composition according to any one of claims 1 to 9, wherein the above component (A) is a diorganopolysiloxane having both ends of the molecular chain blocked with silanol groups represented by the following general formula (2) and / or a diorganopolysiloxane having one end of the molecular chain blocked with a silanol group represented by the following general formula (3). 【Chemical 1】 (In formula (2), R 3 is a monovalent hydrocarbon group having 1 to 12 carbon atoms, which is unsubstituted or substituted and independent of each other, A is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, and m is an integer such that the viscosity of this diorganopolysiloxane at 23 ° C is 100 to 1,000,000 mPa·s.) 【Chemical formula 2】 (In formula (3), R 3 , A is the same as in formula (2), and n is an integer such that the viscosity of this organopolysiloxane at 23 °C is 100 to 1,000,000 mPa·s.)

11. The following general formula (1) R 1 4-a Si(OR 2 ) a (1) (In the formula, R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, R 2 is each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a is 3 or 4.) A hydrolyzable organosilane compound represented by and / or its partial hydrolyzate: 100 parts by mass, Hydroxylamine compound: 0.1 to 50 parts by mass, and An organic divalent tin compound, or a mixture of an organic divalent tin compound and an organic tetravalent tin compound: 0.01 to 20 parts by mass An end-capping agent for end-capping the terminal silanol groups of an organopolysiloxane having both ends and / or one end of the molecular chain blocked with silanol groups, which is used as a base polymer of a room-temperature curable organopolysiloxane composition.

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