Room temperature curable organopolysiloxane composition, method for producing same, and article

Abstract

To provide a room temperature curable organopolysiloxane composition which is easily produced and has excellent preservability without causing sudden thickening or gelation during producing the composition and a method for producing the same.SOLUTION: There is provided a room temperature curable organopolysiloxane composition which comprises (A) a reaction mixture comprising (A1) an organopolysiloxane in which a molecular chain terminal is blocked with a silanol group and (A2) an organic silicon compound of the following formula (1) (R1 and R2 are an unsubstituted or substituted monovalent hydrocarbon group, R3 is H or R1, a is 1 to 3, b is 1 or 2, a+b is 2 to 4) and containing an organopolysiloxan in which the silanol group of (A1) is blocked with a hydrolyzable organosilyl group of (A2), (B) a hydrolyzable organosilane compound of the following formula (2) and / or a partially hydrolyzed condensate thereof, R44-cSi(OR5)c (2) (R4 and R5 are an unsubstituted or substituted monovalent hydrocarbon group, c is 3 or 4) and (C) a curing catalyst.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a room-temperature-curable organopolysiloxane composition (room-temperature-curable silicone resin composition) in which the starting material for the main component (base polymer) is an organopolysiloxane (i.e., a polymer having, as the main chain, an organopolysiloxane structure composed of repeating diorganosiloxane units and whose molecular chain ends are blocked with silanol groups) having, at the molecular chain terminal, a silicon atom bonded to a hydroxyl group (i.e., a silanol group) as a silicon group capable of crosslinking by forming a siloxane bond (hereinafter also referred to as a "reactive silicon group"); the present invention also relates to a method for producing the room-temperature-curable organopolysiloxane composition; coating agents, adhesives, and sealants comprising the room-temperature-curable organopolysiloxane composition; and articles coated, bonded, or sealed with a cured product of the room-temperature-curable organopolysiloxane composition. [Background technology]

[0002] Polymers containing reactive silicon groups undergo hydrolysis and condensation in the presence of moisture. These polymers crosslink and cure in the presence of moisture, allowing them to be used as curable resin compositions. Among these polymers, those whose main chains are silicon-containing compounds (particularly organopolysiloxanes) are generally known as silicone polymers. Curable resin compositions using these polymers are liquid at room temperature and characteristically become rubbery elastic bodies upon curing. Taking advantage of this characteristic, they are widely used as room-temperature-curable organopolysiloxane compositions in coatings, adhesives, construction sealants, and the like. Room-temperature-curable organopolysiloxane compositions are often classified by the compounds released from the composition upon contact with moisture in the air. Representative examples include deacetic acid-, deoxime-, deamido-, dehydroxylamine-, deacetone-, and dealcohol-type organopolysiloxane compositions. Among these, dealcohol-reducing organopolysiloxane compositions, which cure by releasing alcohol, are particularly preferred for their low odor, non-corrosion to metals such as copper and iron, excellent self-adhesion (adhesion to various substrates after curing when no primer is used), and excellent adhesive durability.

[0003] To obtain a dealcohol-removing organopolysiloxane composition, it is necessary to use an organopolysiloxane that has been terminally blocked in advance with alkoxysilyl groups as the base polymer, or to use an organopolysiloxane whose terminal functional groups are silanol groups as the starting material and then terminally block the organopolysiloxane with a silane compound having an alkoxy group during the production process. While using an organopolysiloxane that has been terminally blocked in advance with alkoxysilyl groups is preferable for ease of production and storage stability, it has drawbacks such as high costs. A commonly known method for end-capping silanol groups during the manufacturing process is to incorporate a basic silane compound, such as an amino group-containing silane, as an end-capping catalyst. Patent Publications 5,888,112 and 6,252,466 (Patent Documents 1 and 2) exemplify the use of a basic silane compound having a guanidine group or a phenylmethanamine group as an end-capping catalyst. However, because the basic silane compound used as the end-capping catalyst is special, this can be economically disadvantageous, and depending on the composition, insufficient end-capping can result in problems such as a sudden increase in viscosity and gelation during manufacturing. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5888112 [Patent Document 2] Patent No. 6252466 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above circumstances, and has as its object the provision of a room-temperature-curable organopolysiloxane composition having excellent storage stability, a method for producing the room-temperature-curable organopolysiloxane composition that is easy to produce and does not undergo sudden thickening or gelation during the production of the composition, coating agents, adhesives, and sealants that contain the room-temperature-curable organopolysiloxane composition, and articles that are coated, adhered, or sealed with a cured product of the room-temperature-curable organopolysiloxane composition. [Means for solving the problem]

[0006] As a result of extensive research conducted by the present inventors to achieve the above object, it has been found that by uniformly mixing (A1) an organopolysiloxane having silanol groups at its terminals with (A2) an organosilicon compound represented by general formula (1) described below, the endcapping reaction proceeds rapidly, resulting in a reaction mixture (A) containing an organopolysiloxane in which the silanol groups at the molecular chain terminals of the organopolysiloxane (A1) are blocked with hydrolyzable organosilyl groups derived from the organosilicon compound (A2), and this reaction mixture (A) The present inventors have found that a room-temperature-curable organopolysiloxane composition comprising (B) a hydrolyzable organosilane compound represented by the general formula (2) described below and / or a partial hydrolysis condensate thereof, and (C) a curing catalyst can be produced using an organopolysiloxane having silanol groups at its terminals as the starting material for the main component (base polymer), without experiencing a sudden increase in viscosity or gelation during the production of the composition, and thus can provide a room-temperature-curable organopolysiloxane composition that is easy to produce and has excellent storage stability, thereby achieving the present invention.

[0007] That is, the present invention provides the following room-temperature-curable organopolysiloxane composition, a method for producing the room-temperature-curable organopolysiloxane composition, a coating agent, adhesive, and sealant comprising the room-temperature-curable organopolysiloxane composition, and an article having a cured product of the room-temperature-curable organopolysiloxane composition. [1] (A) (A1) 100 parts by mass of an organopolysiloxane having both molecular chain terminals capped with silanol groups and / or an organopolysiloxane having one molecular chain terminal capped with a silanol group, and (A2) an organosilicon compound represented by the following general formula (1): 0.01 to 30 parts by mass [ka] (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 2 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 3 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, a is an integer of 1 to 3, b is 1 or 2, and a+b is an integer of 2 to 4. a reaction mixture comprising an organopolysiloxane (A1) in which silanol groups at the molecular chain terminals of the organopolysiloxane (A2) are blocked with hydrolyzable organosilyl groups derived from the organosilicon compound (A3) and represented by the following formula: [ka] (In the formula, R 1 , R 2 , R 3 , a, b are the same as above.) (B) 0.01 to 30 parts by mass of a hydrolyzable organosilane compound represented by the following general formula (2) and / or a partial hydrolysis condensate thereof (excluding the component (A2)), and R 4 4-c Si(OR 5 ) c (2) (In the formula, R 4 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 5 are independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and c is 3 or 4. (C) Curing catalyst: 0.001~20 parts by mass A room-temperature-curable organopolysiloxane composition comprising: [2] Furthermore, per 100 parts by mass of the component (A1), (D) isocyanate compound: 0.01 to 10 parts by mass, (E) silylating agent: 0.01 to 10 parts by mass, (F) filler: 1 to 1,000 parts by mass, (G) adhesion promoter (excluding components (A2), (B), (C), and (D)): 0.1 to 30 parts by mass, and (H) Plasticizer: 1 to 1,000 parts by mass The room-temperature-curable organopolysiloxane composition according to [1], which contains one or more compounds selected from the following: [3] The room-temperature-curable organopolysiloxane composition according to [1] or [2], wherein component (A2) is a dehydrocondensation reaction product of a hydrolyzable (organo)hydrosilane compound and a diorganohydroxylamine compound. [4] The room-temperature-curable organopolysiloxane composition according to any one of [1] to [3], wherein the component (A1) is a diorganopolysiloxane represented by the following general formula (3) in which both molecular chain terminals are blocked with silanol groups and / or a diorganopolysiloxane represented by the following general formula (4) in which one molecular chain terminal is blocked with a silanol group: [ka] (In the formula, R 6 are independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, A is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, and k is an integer that gives the diorganopolysiloxane a viscosity at 23°C of 100 to 1,000,000 mPa s. [ka] (In the formula, R 6 A is the same as in formula (3), and m is an integer that gives the diorganopolysiloxane a viscosity of 100 to 1,000,000 mPa·s at 23°C. [5] (A) (A1) 100 parts by mass of an organopolysiloxane having both molecular chain terminals capped with silanol groups and / or an organopolysiloxane having one molecular chain terminal capped with a silanol group, and (A2) an organosilicon compound represented by the following general formula (1): 0.01 to 30 parts by mass [ka] (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 2 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 3 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, a is an integer of 1 to 3, b is 1 or 2, and a+b is an integer of 2 to 4. a reaction mixture comprising an organopolysiloxane (A1) in which silanol groups at the molecular chain terminals of the organopolysiloxane (A2) are blocked with hydrolyzable organosilyl groups derived from the organosilicon compound (A3) and represented by the following formula: [ka] (In the formula, R 1 , R 2 , R 3 , a, b are the same as above.) (B) 0.01 to 30 parts by mass of a hydrolyzable organosilane compound represented by the following general formula (2) and / or a partial hydrolysis condensate thereof (excluding the component (A2)), and R 4 4-c Si(OR 5 ) c (2) (In the formula, R 4 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 5 are independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and c is 3 or 4. (C) Curing catalyst: 0.001~20 parts by mass A method for producing a room-temperature-curable organopolysiloxane composition comprising: [i]: A step of uniformly mixing the (A1) component, the (A2) component, and a part or all of the (B) component (provided that the (C) component is not included in the step [i]), and [ii]: A step of blending the remainder of component (B) and component (C) with the mixture. A method for producing a room-temperature-curable organopolysiloxane composition comprising: [6] [5] A method for producing a room-temperature-curable organopolysiloxane composition according to [5], wherein in step [i], a reaction mixture (A) is prepared which contains an organopolysiloxane in which silanol groups at the molecular chain terminals of the organopolysiloxane in component (A1) have been blocked with hydrolyzable organosilyl groups derived from the organosilicon compound in component (A2) and represented by the following formula: [ka] (In the formula, R 1 , R 2 , R 3 , a, b are the same as above.) [7] The method for producing a room-temperature-curable organopolysiloxane composition according to [5] or [6], wherein 10 to 100 mass% of the total component (B) is blended in step [i], and 0 to 90 mass% of the total component (B) is blended in step [ii]. [8] Furthermore, per 100 parts by mass of the component (A1), (D) isocyanate compound: 0.01 to 10 parts by mass, (E) silylating agent: 0.01 to 10 parts by mass, (F) filler: 1 to 1,000 parts by mass, (G) adhesion promoter (excluding components (A2), (B), (C), and (D)): 0.1 to 30 parts by mass, and (H) Plasticizer: 1 to 1,000 parts by mass The method for producing a room-temperature-curable organopolysiloxane composition according to any one of [5] to [7], wherein one or more selected from the following are blended together or in portions in at least one step selected from before step [i], step [i], step [ii], and after step [ii]. [9] The method for producing a room-temperature-curable organopolysiloxane composition according to any one of [5] to [8], wherein component (A2) is a dehydrocondensation reaction product of a hydrolyzable (organo)hydrosilane compound and a diorganohydroxylamine compound.

[10] The method for producing a room-temperature-curable organopolysiloxane composition according to any one of [5] to [9], wherein the component (A1) is a diorganopolysiloxane represented by the following general formula (3) in which both molecular chain terminals are blocked with silanol groups and / or a diorganopolysiloxane represented by the following general formula (4) in which one molecular chain terminal is blocked with a silanol group: [ka] (In the formula, R 6 are independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, A is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, and k is an integer that gives the diorganopolysiloxane a viscosity at 23°C of 100 to 1,000,000 mPa s. [ka] (In the formula, R 6 A is the same as in formula (3), and m is an integer that gives the diorganopolysiloxane a viscosity of 100 to 1,000,000 mPa·s at 23°C.

[11] A coating agent comprising the room-temperature-curable organopolysiloxane composition according to any one of [1] to [4].

[12] An adhesive comprising the room-temperature-curable organopolysiloxane composition according to any one of [1] to [4].

[13] A sealant comprising the room-temperature-curable organopolysiloxane composition according to any one of [1] to [4].

[14] An article having a coating layer made of a cured product of the room-temperature-curable organopolysiloxane composition according to any one of [1] to [4].

[15] An article bonded and / or sealed with a cured product of the room-temperature-curable organopolysiloxane composition according to any one of [1] to [4]. [Effects of the Invention]

[0008] The room-temperature-curable organopolysiloxane composition of the present invention uses an organopolysiloxane having silanol groups at its terminals as the starting material for the main component (base polymer). By uniformly mixing this organopolysiloxane having silanol groups at its terminals with an unsubstituted or substituted aminoxy group-containing hydrolyzable (organo)silane compound, preferably a dehydrocondensation reaction product of a hydrolyzable (organo)hydrosilane compound and a diorganohydroxylamine compound, the end-capping reaction proceeds rapidly. By adding a curing catalyst after the end-capping reaction, it is possible to obtain a room-temperature-curable organopolysiloxane composition that is easy to produce and has excellent storage stability, without causing a sudden increase in viscosity or gelation during production of the composition. DETAILED DESCRIPTION OF THE INVENTION

[0009] The room-temperature-curable organopolysiloxane composition of the present invention will now be described in more detail.

[0010] [Room-temperature-curable organopolysiloxane composition] The room-temperature-curable organopolysiloxane composition of the present invention contains the following component (A) (a reaction mixture of components (A1) and (A2)), component (B), component (C), and, as needed, components (D) to (H). (A) (A1) an organopolysiloxane having both molecular chain terminals capped with silanol groups and / or an organopolysiloxane having one molecular chain terminal capped with a silanol group, and (A2) An organosilicon compound represented by the following general formula (1): [ka] (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 2are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 3 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, a is an integer of 1 to 3, b is 1 or 2, and a+b is an integer of 2 to 4. a reaction mixture comprising an organopolysiloxane (A1) in which silanol groups at the molecular chain terminals of the organopolysiloxane (A2) are blocked with hydrolyzable organosilyl groups derived from the organosilicon compound (A3) and represented by the following formula: [ka] (In the formula, R 1 , R 2 , R 3 , a, b are the same as above.) (B) a hydrolyzable organosilane compound represented by the following general formula (2) and / or a partial hydrolysis condensate thereof (excluding component (A2)), R 4 4-c Si(OR 5 ) c (2) (In the formula, R 4 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 5 are independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and c is 3 or 4. (C) curing catalyst, (D) isocyanate compounds, (E) a silylating agent, (F) filler, (G) adhesion promoters (excluding components (A2), (B), (C), and (D)), and (H) Plasticizer.

[0011] (A1) Ingredients: The component (A1) used in the room-temperature-curable organopolysiloxane composition of the present invention is an organopolysiloxane in which both molecular chain terminals are capped with silanol groups (hydroxyl groups bonded to silicon atoms) and / or an organopolysiloxane in which one molecular chain terminal is capped with a silanol group (hydroxyl group bonded to a silicon atom) (i.e., one or more essentially linear polymers having as their main chain an organopolysiloxane structure consisting of repeating diorganosiloxane units in which both molecular chain terminals are capped with silanol groups or in which one molecular chain terminal is capped with a silanol group and the other terminal is preferably capped with a trialkylsilyl group), and is the starting material for the main component (base polymer) of the room-temperature-curable organopolysiloxane composition of the present invention.

[0012] Specific examples of component (A1) include an essentially linear diorganopolysiloxane represented by the following general formula (3) in which both molecular chain terminals are blocked with silanol groups, and / or an essentially linear diorganopolysiloxane represented by the following general formula (4) in which one molecular chain terminal is blocked with a silanol group. [ka] (In the formula, R 6 are 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 k is an integer that gives the diorganopolysiloxane a viscosity of 100 to 1,000,000 mPa s at 23°C. [ka] (In the formula, R 6 A is the same as in formula (3), and m is an integer that gives the diorganopolysiloxane a viscosity of 100 to 1,000,000 mPa·s at 23°C.

[0013] Here, in the general formulas (3) and (4), R 6Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; vinyl, allyl, propenyl, and isopropenyl groups; Examples of suitable alkyl groups include alkenyl groups such as phenyl, tolyl, xylyl, α-, β-naphthyl, and the like; aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl; and groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as F, Cl, and Br, or with cyano groups, such as 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl. Among these, those excluding aliphatic unsaturated hydrocarbon groups such as alkenyl groups are preferred, and alkyl groups such as methyl and ethyl groups, and aryl groups such as phenyl groups are more preferred, with methyl being particularly preferred.

[0014] In the general formulas (3) and (4), A is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, preferably 2 to 4 carbon atoms, and the divalent hydrocarbon group is -(CH2) p -or-(CH=CH) q Preferred are alkylene and alkenylene groups such as - (p represents an integer of 1 to 8, preferably an integer of 1 to 4, and q represents an integer of 1 to 4). Among these, an oxygen atom, -CH2CH2-, -CH2CH2CH2-, and -CH=CH- are preferred.

[0015] In the general formulas (3) and (4), k and m are each integers that provide a viscosity of the diorganopolysiloxane at 23°C of 100 to 1,000,000 mPa s. Typically, k and m are integers from 20 to 2,000, preferably from 20 to 1,600, more preferably from 20 to 1,000, and even more preferably from about 20 to 500. 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 particularly preferably 1,000 to 100,000 mPa·s. The viscosity is measured using a rotational viscometer (e.g., BL type, BH type, BS type, cone-plate type, etc.) (the same applies hereinafter). Furthermore, the disiloxane units (R 6 )2SiO 2 / 2 The k and m values, which indicate the number of repetitions (or degree of polymerization) of the 2-amino-2-methyl-1, ...

[0016] Specific examples of the component (A1) include the following: [ka] (In each formula, R 6 , k is the same as above.) [ka] (In each formula, R 6 , m is the same as above.)

[0017] The organopolysiloxane of component (A1) in which both molecular chain terminals are blocked with silanol groups and / or the organopolysiloxane in which one molecular chain terminal is blocked with silanol groups can be used either alone or in combination of two or more types with different structures or degrees of polymerization.

[0018] (A2) Ingredients: The component (A2) used in the room-temperature-curable organopolysiloxane composition of the present invention is used to cap (substitute) with hydrolyzable organosilyl groups the terminal silanol groups of the organopolysiloxane of component (A1) in which both molecular chain terminals are capped with silanol groups and / or the organopolysiloxane in which one molecular chain terminal is capped with silanol groups. The component (A2) is an organosilicon compound represented by the following general formula (1) (i.e., an unsubstituted or substituted aminoxy group-containing hydrolyzable (organo)silane compound): [ka] (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 2 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 3 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, a is an integer of 1 to 3, b is 1 or 2, and a+b is an integer of 2 to 4.

[0019] Here, in the general formula (1), R 1Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; and alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, and hexenyl. aryl groups such as phenyl, tolyl, xylyl, and α- and β-naphthyl; aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl; and alkyl groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as F, Cl, and Br, alkoxy groups such as methoxy and ethoxy, and cyano groups, for example, 3-chloropropyl, 3,3,3-trifluoropropyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, and 2-cyanoethyl. Among these, those excluding aliphatic unsaturated hydrocarbon groups such as alkenyl groups are preferred, and alkyl groups such as methyl and ethyl groups, α-alkoxy-substituted alkyl groups such as methoxymethyl and ethoxymethyl groups, and aryl groups such as phenyl groups are more preferred, with methyl and methoxymethyl groups being particularly preferred.

[0020] In the general formula (1), R 2Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; vinyl, allyl, propenyl, and isopropenyl groups; Examples of suitable alkyl groups include alkenyl groups such as phenyl, tolyl, xylyl, α-, β-naphthyl, and the like; aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl; and groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as F, Cl, and Br, or with cyano groups, such as 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl. Among these, those excluding aliphatic unsaturated hydrocarbon groups such as alkenyl groups are preferred, and alkyl groups such as methyl and ethyl groups, and aryl groups such as phenyl groups are more preferred, with methyl and ethyl groups being particularly preferred.

[0021] In the general formula (1), R 3Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; vinyl, allyl, propenyl, and isopropenyl groups; Examples include alkenyl groups such as phenyl, tolyl, xylyl, α-, β-naphthyl, and the like; aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl, and groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as F, Cl, and Br, or with cyano groups, for example, 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl. Among these, alkyl groups such as methyl and ethyl, and aryl groups such as phenyl are preferred, with the ethyl group being particularly preferred due to the ease of availability of raw materials.

[0022] In the general formula (1), a is an integer of 1 to 3, preferably 2 or 3; b is 1 or 2, preferably 1; and a+b is an integer of 2 to 4, preferably 3 or 4.

[0023] The organosilicon compound represented by the general formula (1) (unsubstituted or substituted aminoxy group-containing hydrolyzable (organo)silane compound) can be prepared by reacting a silane compound represented by the following formula (5) (hydrolyzable (organo)hydrosilane compound) with: [ka] (In the formula, R 1 , R 2 , a and b are the same as in general formula (1). an unsubstituted or substituted hydroxylamine compound represented by the following formula (6): [ka] (In the formula, R 3 is the same as general formula (1). It can be obtained by the dehydrogenation condensation reaction of the above.

[0024] Examples of the silane compound (hydrolyzable (organo)hydrosilane compound) represented by formula (5) include diorganoxyorganosilane compounds such as dialkoxyorganosilane compounds, such as dimethoxymethylsilane, dimethoxyethylsilane, dimethoxyvinylsilane, dimethoxyphenylsilane, dimethoxy(methoxymethyl)silane, dimethoxy(ethoxymethyl)silane, diethoxymethylsilane, diethoxyethylsilane, diethoxyvinylsilane, diethoxyphenylsilane, diethoxy(methoxymethyl)silane, and diethoxy(ethoxymethyl)silane; and triorganoxysilane compounds such as trialkoxysilane compounds, such as trimethoxysilane and triethoxysilane.

[0025] Examples of the unsubstituted or substituted hydroxylamine compound represented by formula (6) include diorganohydroxylamine compounds such as hydroxylamine and dialkylhydroxylamines such as dimethylhydroxylamine, diethylhydroxylamine, and methylethylhydroxylamine.

[0026] The organosilicon compound represented by the above general formula (1) (unsubstituted or substituted aminoxy group-containing hydrolyzable (organo)silane compound) is preferably a dehydrocondensation reaction product of a hydrolyzable (organo)hydrosilane compound and a diorganohydroxylamine compound.

[0027] In the above-mentioned dehydrocondensation reaction, the reaction ratio of the unsubstituted or substituted hydroxylamine compound represented by formula (6) is preferably 1 to 2 moles, and more preferably 1.0 to 1.2 moles, per mole of SiH groups in the silane compound represented by formula (5) (hydrolyzable (organo)hydrosilane compound).

[0028] The dehydrocondensation reaction conditions are preferably 0 to 100°C, particularly 30 to 70°C, for 5 minutes to 5 hours, particularly 1 to 3 hours.

[0029] Specific examples of the organosilicon compound (unsubstituted or substituted aminoxy group-containing hydrolyzable (organo)silane compound) of component (A2) include the following compounds. [ka]

[0030] The amount of component (A2) blended is preferably 0.01 to 30 parts by mass, particularly 0.05 to 10 parts by mass, and especially 0.1 to 3 parts by mass, per 100 parts by mass of component (A1). If the amount of component (A2) is too small, the end-capping reaction of the terminal silanol groups of component (A1) will not proceed efficiently, while if the amount is too large, problems such as poor storage stability and economical disadvantages will arise.

[0031] (A) Component: The component (A) of the room-temperature-curable organopolysiloxane composition of the present invention is a reaction mixture comprising the aforementioned components (A1) and (A2), and containing an organopolysiloxane (base polymer) in which the silanol groups at the molecular chain terminals of the organopolysiloxane of component (A1) have been blocked with hydrolyzable organosilyl groups derived from the organosilicon compound of component (A2), as shown below: [ka] (In the formula, R 1 , R 2 , R 3 , a, b are the same as above.)

[0032] The organopolysiloxane in which the silanol groups at the molecular chain terminals of the organopolysiloxane of component (A1), which serves as the main component (base polymer) of the room-temperature-curable organopolysiloxane composition of the present invention, are blocked with hydrolyzable organosilyl groups of the above formula derived from the organosilicon compound of component (A2), can be prepared by uniformly mixing the above-described components (A1) and (A2) in an environment that does not contain the component (C), which will be described later, and the terminal blocking reaction proceeds rapidly.

[0033] (B) Ingredients: The room-temperature-curable organopolysiloxane composition of the present invention contains, as component (B), a hydrolyzable organosilane compound represented by the following general formula (2) and / or a partial hydrolysis condensate thereof (excluding component (A2)). In the room-temperature-curable organopolysiloxane composition of the present invention, component (B) acts as a crosslinking agent (curing agent) that forms a crosslinked structure. R 4 4-c Si(OR 5 ) c (2) (In the formula, R 4 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 5 are independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and c is 3 or 4.

[0034] Here, in the general formula (2), R 4Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; vinyl, allyl, propenyl, and isopropenyl groups; Examples include alkenyl groups such as phenyl, tolyl, xylyl, α-, β-naphthyl, and the like; aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl; and groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as F, Cl, and Br, or with cyano or methoxy groups, such as 3-chloropropyl, 3,3,3-trifluoropropyl, 2-cyanoethyl, and methoxymethyl. Among these, alkyl groups such as methyl and ethyl groups, alkenyl groups such as vinyl, and methoxymethyl groups in which one hydrogen atom of a methyl group has been substituted with a methoxy group are preferred, with methyl being particularly preferred.

[0035] In the general formula (2), R 5Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; vinyl, allyl, propenyl, and isopropenyl groups; Examples include alkenyl groups such as phenyl, tolyl, xylyl, α-, β-naphthyl, and the like; aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl; and groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as F, Cl, and Br, or with cyano and methoxy groups, such as 3-chloropropyl, 3,3,3-trifluoropropyl, 2-cyanoethyl, and methoxymethyl. Among these, alkyl groups such as methyl and ethyl are more preferred, with methyl being particularly preferred.

[0036] Examples of component (B) include (organo)silane compounds having three or four hydrolyzable groups such as alkoxy groups in the molecule, and their partial hydrolysis condensates (i.e., (organo)siloxane oligomers having three or more residual hydrolyzable groups in the molecule, obtained by partial hydrolysis condensation of the (organo)silane compounds), and specific examples thereof include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, methyl silicate, and ethyl silicate, and their partial hydrolysis condensates, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriisopropylsilane.

[0033] Examples of organotrialkoxysilanes include organotrialkoxysilanes such as ethoxysilane, methyltris(methoxyethoxy)silane, vinyltris(methoxyethoxy)silane, methoxymethyltrimethoxysilane, methoxymethyltriethoxysilane, ethoxymethyltrimethoxysilane, ethoxymethyltriethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, and decyltrimethoxysilane, and their partial hydrolysis condensates. Particularly preferred are tetramethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, methoxymethyltrimethoxysilane, and their hydrolysis condensates, but are not limited to these. These can be used alone or in combination of two or more.

[0037] The amount of the hydrolyzable organosilane compound and / or its partial hydrolysis condensate (B) blended per 100 parts by mass of the above-mentioned (A1) component is 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass. If the amount of component (B) is too small, sufficient rubber properties may not be obtained even after curing the composition, while if the amount is too large, rapid curing properties may be impaired or it may be economically disadvantageous.

[0038] (C) Ingredients: Component (C) of the present invention is a curing catalyst (non-metallic organic catalyst and / or metallic catalyst) that acts to accelerate the curing of the room-temperature-curable organopolysiloxane composition of the present invention.

[0039] The non-metallic organic catalyst used as the curing catalyst may be any known curing accelerator for condensation-curable organopolysiloxane compositions, and is not particularly limited. Examples of the non-metallic organic catalyst include phosphazene-containing compounds such as N,N,N',N',N'',N''-hexamethyl-N'''-(trimethylsilylmethyl)phosphorimidic triamide; amine compounds or salts thereof such as hexylamine and dodecylamine phosphate; quaternary ammonium salts such as benzyltriethylammonium acetate; and guanidyl group-containing silanes and siloxanes such as tetramethylguanidylpropyltrimethoxysilane, tetramethylguanidylpropylmethyldimethoxysilane, and tetramethylguanidylpropyltris(trimethylsiloxy)silane. Furthermore, the non-metallic organic catalyst may be used alone or in combination with two or more different catalysts.

[0040] The metal catalyst used as the curing catalyst may be any known curing accelerator for condensation-curable organopolysiloxane compositions, and is not particularly limited. Examples include alkyltin(IV) ester compounds such as dibutyltin(IV) diacetate, dibutyltin(IV) dilaurate, dibutyltin(IV) dioctoate, dioctyltin(IV) dineodecanoate, and di-n-butyl-dimethoxytin(IV); titanate esters or titanium chelate compounds such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetonato)titanium, titanium isopropoxyoctylene glycol, and titanium diisopropoxybis(ethylacetoacetate); and aluminum alcoholates such as aluminum isopropylate and aluminum secondary butylate. Examples of metal catalysts include, but are not limited to, aluminum compounds, aluminum chelate compounds such as aluminum alkyl acetate diisopropylate and aluminum bis(ethylacetoacetate) monoacetylacetonate, organometallic compounds such as zinc naphthenate, zinc stearate, zinc 2-ethyloctoate, iron 2-ethylhexoate, cobalt 2-ethylhexoate, manganese 2-ethylhexoate, cobalt naphthenate, bismuth(III) neodecanoate, bismuth(III) 2-ethylhexanoate, bismuth(III) citrate, and bismuth octoate, and alkali metal salts of lower fatty acids such as potassium acetate, sodium acetate, and lithium oxalate. Metal catalysts may be used singly or in combination.

[0041] The amount of the curing catalyst for component (C) is 0.001 to 20 parts by mass, preferably 0.01 to 10 parts by mass, per 100 parts by mass of component (A1). If the amount of component (C) is too small, sufficient curability cannot be obtained, while if the amount is too large, the curing reaction proceeds too quickly, resulting in insufficient working time and being economically disadvantageous.

[0042] (D) Ingredients: Component (D) of the present invention is an isocyanate compound, and is an optional component that can be incorporated into the room-temperature-curable organopolysiloxane composition of the present invention as needed. It acts as a scavenger for the hydroxylamine that is by-produced in the end-capping reaction with component (A2), and thus improves the storage stability of the room-temperature-curable organopolysiloxane composition of the present invention.

[0043] Examples of the isocyanate compound include monoisocyanates such as hexyl isocyanate, phenyl isocyanate, trimethoxysilylpropyl isocyanate, triethoxysilylpropyl isocyanate, and paratoluenesulfonyl isocyanate; diisocyanates such as p-phenylene diisocyanate, toluene diisocyanate, 4,4'-diphenylmethylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate; and other polyisocyanates. From the viewpoint of dispersibility in the composition, however, silane-modified isocyanates are preferred, and trimethoxysilylpropyl isocyanate and triethoxysilylpropyl isocyanate are particularly preferred.

[0044] The amount of the isocyanate compound (D) blended is 0.01 to 10 parts by mass, and preferably 0.1 to 5 parts by mass, per 100 parts by mass of the above-mentioned (A1) component. If the amount of component (D) is too small, the desired effects may not be obtained, while if the amount is too large, it is economically disadvantageous.

[0045] (E) Ingredients: Component (E) of the present invention is a silylating agent, an optional component that is incorporated into the room-temperature-curable organopolysiloxane composition of the present invention as needed. This component further improves the storage stability of the room-temperature-curable organopolysiloxane composition of the present invention and imparts good mechanical properties to a cured product of the room-temperature-curable organopolysiloxane composition of the present invention that has been stored in a sealed container for extended periods of time.

[0046] Examples of the silylating agent include organosilazane compounds such as hexamethyldisilazane and divinyltetramethyldisilazane, organosilylurea compounds such as N,N-bis(trimethylsilyl)urea, N,O-bis(trimethylsilyl)acetamide, O-methyl-O-trimethylsilylmethylketene acetal, and N-trimethylsilyldiethylamine. Any compound can be used as long as it is capable of silylating alcoholic hydroxyl groups (C-OH groups) and does not adversely affect the properties of the room-temperature-curable organopolysiloxane composition of the present invention. Organosilazane compounds and organosilylurea compounds are preferred.

[0047] The amount of the silylating agent (E) is in the range of 0.01 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of the component (A1). If the amount of component (E) is too small, the desired effect may not be obtained, whereas if the amount is too large, the odor may become strong and it may be economically disadvantageous.

[0048] (F) Ingredients: Component (F) is a filler (an inorganic filler and / or an organic resin filler), which is an optional component that is incorporated into the room-temperature-curable organopolysiloxane composition of the present invention as needed, and is used to impart sufficient mechanical strength to the cured product formed from this composition. Known fillers can be used, including inorganic fillers such as reinforcing silica fillers (fine powder silica, fumed silica (fumed silica or dry silica), precipitated silica (wet silica), and silica whose surface has been hydrophobized with an organosilicon compound; glass beads, glass balloons, transparent resin beads, silica aerogel, diatomaceous earth, metal oxides (such as iron oxide, zinc oxide, titanium oxide, and fumed metal oxide); quartz powder (crystalline silica); reinforcing agents (such as carbon black, talc, zeolite, and bentonite); asbestos, glass fiber, carbon fiber, calcium carbonate (such as colloidal calcium carbonate and heavy calcium carbonate), metal carbonates (such as magnesium carbonate and zinc carbonate), glass wool, finely powdered mica, and fused silica powder; and organic resin fillers such as synthetic resin powders (such as polystyrene, polyvinyl chloride, and polypropylene). Among these fillers, inorganic fillers such as silica, calcium carbonate, and zeolite are preferred, with fumed silica and calcium carbonate whose surface has been hydrophobized being particularly preferred.

[0049] When a filler of component (F) is blended, the blending amount is preferably 1 to 1,000 parts by mass, particularly 5 to 400 parts by mass, per 100 parts by mass of component (A1). The cured product obtained from this composition tends to exhibit sufficient mechanical strength when blended rather than when not blended, but if more than 1,000 parts by mass is used, not only does the viscosity of the composition increase, making workability difficult, but the rubber strength after curing tends to decrease, making it difficult to obtain rubber elasticity.

[0050] (G) Ingredients: Component (G) is an adhesion promoter (excluding components (A2), (B), (C), and (D)), and is an optional component that is incorporated into the room-temperature-curable organopolysiloxane composition of the present invention as needed, and is used to impart sufficient adhesion to the cured product formed from this composition. Specifically, it is preferable to blend hydrolyzable organosilane compounds (so-called carbon functional silanes or silane coupling agents) having in the molecule a monovalent hydrocarbon group containing a functional group (excluding aminoxy groups, guanidyl groups, and isocyanate groups) having a heteroatom such as a nitrogen atom, oxygen atom, or sulfur atom in addition to the hydrolyzable group, such as aminosilanes such as γ-aminopropyltriethoxysilane and 3-2-(aminoethylamino)propyltrimethoxysilane [also known as N-2-(aminoethyl)-3-aminopropyltrimethoxysilane], epoxysilanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, (meth)acrylic silanes such as γ-(meth)acryloxypropyltrimethoxysilane and γ-(meth)acryloxypropyltriethoxysilane, and mercaptosilanes such as γ-mercaptopropyltrimethoxysilane. The adhesion promoter (carbon functional silane or silane coupling agent) of component (G) contains a monovalent hydrocarbon group in the molecule that contains a functional group (excluding aminoxy, guanidyl, and isocyanate groups) that has a heteroatom such as a nitrogen atom, oxygen atom, or sulfur atom in addition to a hydrolyzable group (however, it does not contain an organooxy-substituted alkyl group such as a methoxymethyl group), and is therefore clearly distinguishable from the organosilicon compounds of component (A2), the hydrolyzable organosilane compounds and / or their partial hydrolysis condensates of component (B), the non-metallic organic catalysts (silanes and siloxanes containing a guanidyl group) of component (C), and the isocyanate compounds of component (D).

[0051] When the adhesion promoter (G) is added, the amount added is preferably 0.1 to 30 parts by mass, and particularly 0.5 to 20 parts by mass, per 100 parts by mass of the component (A1). If the amount exceeds 30 parts by mass, the curability may be insufficient or it may be economically disadvantageous.

[0052] (H) Component: Component (H) is a plasticizer, an optional component that may be incorporated into the room-temperature-curable organopolysiloxane composition of the present invention as needed, and it allows the viscosity of the composition to be adjusted to a level that is easy to handle during application, without impairing the mechanical properties or flame retardancy of the cured product formed from the composition.

[0053] Examples of plasticizers that can be used in the room-temperature-curable organopolysiloxane composition of 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 esters, dioctyl adipate (DOA), diisononyl adipate (DINA), and the like. ), diisodecyl adipate (DIDA), di-n-alkyl adipate, dibutyl diglycol adipate (BXA), bis(2-ethylhexyl) azelaate (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), tri(chloroethyl) phosphite phosphate (TCEP), tris(dichloropropyl)phosphate (CPP), tributoxyethyl phosphate (TBXP), tris(β-chloropropyl)phosphate (TMCPP), triphenyl phosphate (TPP), octyldiphenyl phosphate (ODP), acetyltriethyl citrate, acetyltributyl citrate, etc. Other plasticizers include trimellitic acid-based plasticizers, polyester-based plasticizers, chlorinated paraffin, stearic acid-based plasticizers, and linear dimethylpolysiloxanes (e.g., hexamethylsiloxane) with both ends of the molecular chain blocked with trimethylsilyl groups. Examples of suitable silicone oils include silicone oils (non-functional organopolysiloxanes) such as branched dimethylpolysiloxanes such as 2-(trimethylsiloxy)-1,1,1,2,3,3,3-heptamethyltrisiloxane, octamethylcyclopentasiloxane, decamethylcyclopentasiloxane, octamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, etc., and cyclic dimethylpolysiloxanes such as octamethylcyclopentasiloxane and decamethylcyclopentasiloxane; and petroleum-based high-boiling point solvents such as polyoxypropylene glycol, paraffin, naphthene, and isoparaffin.These may be used alone or in combination of two or more. Among these, silicone oil (non-functional organopolysiloxane) is particularly preferred.

[0054] As the silicone oil (non-functional organopolysiloxane), an organopolysiloxane represented by the following general formula (7) can be preferably used.

[0055] [ka] (In the formula, R 7 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms that do not contain aliphatic unsaturated bonds, and n is an integer that gives the organopolysiloxane a viscosity of 1.5 to 1,000,000 mPa s at 23°C.

[0056] In the general formula (7), R 7 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, that do not contain an aliphatic unsaturated bond, and specifically include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, and decyl, aryl groups such as phenyl, tolyl, xylyl, and naphthyl, aralkyl groups such as benzyl, phenylethyl, and phenylpropyl, and groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as F, Cl, or Br, such as chloromethyl, chloropropyl, bromoethyl, and trifluoropropyl. Among these, groups excluding aliphatic unsaturated hydrocarbon groups such as alkenyl groups are preferred, alkyl groups such as methyl and ethyl groups, and aryl groups such as phenyl groups are more preferred, with methyl being particularly preferred.

[0057] In the organopolysiloxane represented by the above formula (7), the value of n, which indicates the number of repetitions of the diorganosiloxane unit (degree of polymerization), may generally be an integer of about 3 to 3,000, preferably 5 to 2,000, and more preferably 10 to 1,000. The viscosity of the organopolysiloxane at 23° C. is preferably 1.5 to 1,000,000 mPa·s, and more preferably 10 to 100,000 mPa·s.

[0058] When component (H) is included, the amount added is preferably 1 to 1,000 parts by mass, more preferably 2 to 500 parts by mass, and even more preferably 3 to 200 parts by mass, per 100 parts by mass of component (A1). When the amount of component (H) is within the above range, it is possible to adjust the viscosity of the room-temperature-curable organopolysiloxane composition of the present invention to one that is easy to handle during application, without impairing the mechanical properties or flame retardancy of the composition, which is preferred.

[0059] [Other ingredients] Furthermore, a thixotropic agent may be blended as an optional additive in the room-temperature-curable organopolysiloxane composition of the present invention, provided that the blend does not impair the object of the present invention. Examples of thixotropy-imparting agents include polyether compounds such as polyethylene oxide (polyoxyethylene), polypropylene oxide (polyoxypropylene), ethylene oxide-propylene oxide copolymers (polyoxyethylene-polyoxypropylene copolymers), and polymers of these compounds whose molecular chain ends (one end or both ends) are blocked with alkyl ethers; silane-modified or silicone-modified polyether compounds; polyether phosphate esters; polyether fatty acid esters; fatty acid amide waxes; hydrogenated castor oil; and oxidized polyolefins.

[0060] The room-temperature-curable organopolysiloxane composition of the present invention may further contain optional additives such as storage stabilizers (storage stability improvers), such as glycerin esters of fatty acids having fatty acid ester groups, such as triacetin, diacetin, monoacetin, tributyrin, tricaprylin, tristearin, and glycerol diacetate laurate, and 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, such as trimethylolpropane tristearate, trimethylolpropane triacetate, and pentaerythritol monoacetate. Other known additives, such as pigments, dyes, antioxidants, antioxidants, antistatic agents, and flame retardants, such as antimony oxide and chlorinated paraffin, may also be incorporated within the scope of the present invention. Furthermore, mildew inhibitors and antibacterial agents may also be incorporated.

[0061] Furthermore, the room-temperature-curable organopolysiloxane composition of the present invention may contain an organic solvent, if necessary. Examples of organic solvents include aliphatic hydrocarbon compounds such as n-hexane, n-heptane, isooctane, and isododecane, and aromatic hydrocarbon compounds such as toluene and xylene. The amount of organic solvent may be adjusted as appropriate within a range that does not impair the effects of the present invention.

[0062] [Method for producing room temperature curable organopolysiloxane composition] The method for producing a room-temperature-curable organopolysiloxane composition of the present invention comprises the steps of: uniformly mixing at least all of component (A1), all of component (A2), and some or all of component (B), excluding component (C), among the above-mentioned components (step [i]); and blending the remainder of component (B) and all of component (C) with the mixture (step [ii]).

[0063] In the method for producing a room-temperature-curable organopolysiloxane composition of the present invention, with respect to steps [i] and [ii], the hydrolyzable organosilane compound and / or its partial hydrolysis condensate of component (B) is preferably blended in step [i] in an amount of 10 to 100 mass%, particularly 30 to 100 mass%, or even 50 to 100 mass% of the total component (B), and in step [ii] in an amount of 0 to 90 mass%, particularly 0 to 70 mass%, or even 0 to 50 mass% of the total component (B). If the blending ratio in step [i] is too low, gelation may occur during the production process, which is disadvantageous. The curing catalyst of component (C) is not blended in the above step [i], but is blended in the above step [ii].

[0064] The above step [i] is a step of terminally blocking an organopolysiloxane (A1) having silanol groups at its terminals. In this step [i], a reaction mixture (A) is prepared which contains an organopolysiloxane (main component (base polymer)) in which the silanol groups at the molecular chain terminals of the organopolysiloxane (A1) have been blocked with hydrolyzable organosilyl groups derived from an organosilicon compound (A2) and represented by the following formula: [ka] (In the formula, R 1 , R 2 , R 3 , a, b are the same as above.)

[0065] In step [i], the components may be mixed under substantially anhydrous conditions, at normal or reduced pressure, and at any temperature (usually 0 to 100°C, preferably 10 to 70°C), for a time period of usually 5 minutes to 5 hours, and preferably 10 minutes to 2 hours.

[0066] After the end-capping step (step [i]), the remainder of component (B) and the entirety of component (C) are blended (step [ii]). Here, component (D), component (E), component (F), component (G), component (H), and other components can be mixed all at once or in portions at least one of the following steps: before step [i], step [i], step [ii], and step [ii]. For example, they may be mixed in step [ii], after step [ii], simultaneously during the end-capping step (step [i]), pre-mixed with component (A1) before the end-capping step (step [i]), or mixed in two or more portions at any of these times. However, when component (G) is an aminosilane, adding it during the end-capping step (step [i]) can cause the mixture to sag, which can be disadvantageous, particularly when used as an adhesive or construction sealant. Therefore, it is preferable to add it after the end-capping step (step [ii]).

[0067] In step [ii], the components may be mixed under substantially anhydrous conditions, at normal or reduced pressure, and at any temperature (usually 0 to 100°C, preferably 10 to 70°C), for a time period of usually 5 minutes to 5 hours, preferably 10 minutes to 2 hours.

[0068] If the end-capping of component (A1) is insufficient in the end-capping step (step [i]), adding components (C) and (G) after the end-capping step (step [ii]) may result in gel formation or increased viscosity, or the storage stability of the resulting composition may be impaired even if no gel formation occurs. However, with a room-temperature-curable organopolysiloxane composition produced under the above-mentioned conditions, the end-capping step proceeds smoothly, allowing the room-temperature-curable organopolysiloxane composition to be produced under mild conditions in an extremely short time using an inexpensive organopolysiloxane having silanol groups as terminal functional groups, and this improves productivity, and the storage stability is also good, making it economically advantageous.

[0069] The room-temperature-curable organopolysiloxane composition of the present invention cures when left in a room temperature environment (23°C±15°C, humidity 50%RH±5%RH), and known molding methods and curing conditions can be used depending on the type of composition. In particular, one-component compositions can be stored in the absence of moisture, i.e., in a sealed container that is moisture-proof, and then readily cure at room temperature (23°C±15°C) by exposing them to moisture in the air when used.

[0070] Furthermore, the resulting cured product exhibits good flexibility and rubber elasticity, making it useful as a coating agent, adhesive, or sealant (for example, a construction sealant). The method for using the room-temperature-curable organopolysiloxane composition of the present invention as a coating agent, adhesive, or sealant can be any conventional method known in the art and is not particularly limited.

[0071] Examples of articles having a coating layer made of a cured product of the room-temperature-curable organopolysiloxane composition of the present invention include articles made of glass, various resins, various metals, etc., but there are no particular restrictions on the material and shape of the substrate.

[0072] Examples of articles that can be bonded and / or sealed with a cured product of the room-temperature-curable organopolysiloxane composition of the present invention include articles made of glass, various metals, etc., but there are no particular restrictions on the material or shape of the substrate. [Example]

[0073] The present invention will be described in detail below with reference to examples and comparative examples, 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 value measured using a rotational viscometer at 23°C. The composition was prepared at a room temperature of 23°C.

[0074] [Synthesis Example 1] Synthesis of organosilicon compounds 1 A 500 ml separable flask was charged with 44.6 g (0.5 mol) of diethylhydroxylamine, and 53.1 g (0.5 mol) of dimethoxymethylsilane was added dropwise while stirring. After the dropwise addition, the mixture was heated and aged in a 50°C oil bath for 2 hours, yielding 92.3 g of the target organosilicon compound 1, represented by the following formula: [ka]

[0075] [Synthesis Example 2] Synthesis of organosilicon compounds 2 The synthesis of organosilicon compound 1 was repeated except that 61.0 g (0.5 mol) of trimethoxysilane was used instead of 53.1 g (0.5 mol) of dimethoxymethylsilane, and 103.6 g of the target organosilicon compound 2 represented by the following formula was obtained. [ka]

[0076] [Example 1] 100 parts of a linear dimethylpolysiloxane having a viscosity of 50,000 mPa·s and both molecular chain ends blocked with silanol groups (in the above formula (3), R 6 = methyl group, A = oxygen atom, k = approximately 850), 40 parts of a linear dimethylpolysiloxane with a viscosity of 100 mPa s and both molecular chain terminals capped with trimethylsilyl groups, 15 parts of fumed silica, and 0.5 parts of a polyether compound (polyoxyethylene-polyoxypropylene copolymer capped with one molecular terminal monobutyl ether) were added and mixed under reduced pressure for 30 minutes. Subsequently, 1.5 parts of organosilicon compound 1 obtained in Synthesis Example 1, 9 parts of methyltrimethoxysilane, and 2 parts of trimethoxysilylpropyl isocyanate were added to the mixture and mixed under reduced pressure for 10 minutes. Next, 0.8 parts of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 0.8 parts of hexamethyldisilazane, and 0.3 parts 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, thereby preparing Composition 1.

[0077] [Example 2] Composition 2 was prepared in the same manner as in Example 1, except that 1.5 parts of organosilicon compound 2 obtained in Synthesis Example 2 was used instead of 1.5 parts of organosilicon compound 1 in Example 1.

[0078] [Example 3] In Example 1, 100 parts of a linear dimethylpolysiloxane having a viscosity of 50,000 mPa s and having both molecular chain terminals terminated with silanol groups and 40 parts of a linear dimethylpolysiloxane having a viscosity of 100 mPa s and having both molecular chain terminals terminated with trimethylsilyl groups were replaced with a linear dimethylpolysiloxane having a viscosity of 20,000 mPa s and having both molecular chain terminals terminated with silanol groups (R 6 = methyl group, A = oxygen atom, k = approximately 650), and 85 parts of a linear dimethylpolysiloxane (R 6 Composition 3 was prepared in the same manner as in Example 1, except that 50 parts of a dimethylpolysiloxane having a viscosity of 20,000 mPa s and both ends capped with trimethylsilyl groups was used.

[0079] [Comparative Example 1] Composition 4 was prepared in the same manner as in Example 1, except that organosilicon compound 1 was not added. However, after adding aminosilane (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane) and tin catalyst (dioctyltin(IV) dineodecanoate), gelation occurred in the system, and composition 4 could not be prepared.

[0080] Comparative Example 2 Composition 5 was prepared in the same manner as in Example 1, except that 1 part of a basic silane compound represented by the following structural formula (8) was used instead of 1.5 parts of organosilicon compound 1. However, after adding aminosilane (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane) and a tin catalyst (dioctyltin(IV) dineodecanoate), gelation occurred in the system, and composition 5 could not be prepared. [ka]

[0081] Comparative Example 3 Composition 6 was prepared in the same manner as in Example 1, except that 0.8 parts of 1,1,3,3-tetramethyl-2-[3-(trimethoxysilyl)propyl]guanidine was used instead of 1.5 parts of organosilicon compound 1. However, after adding aminosilane (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane) and tin catalyst (dioctyltin(IV) dineodecanoate), gelation occurred in the system, and composition 6 could not be prepared.

[0082] [Evaluation test] The tack-free time of each of the compositions prepared in Examples 1 to 3 was measured immediately after preparation. Immediately after preparation, each composition prepared in Examples 1 to 3 was molded into a 2 mm thick sheet, exposed to air at 23°C and 50% RH, and then the sheet was left in the same atmosphere for 7 days. The physical properties of the resulting cured product (initial physical properties: hardness, elongation at break, and tensile strength) were measured in accordance with JIS K-6249. The hardness was measured using a Durometer A hardness tester according to JIS K-6249.

[0083] [Storage stability] Each composition prepared in Examples 1 to 3 was placed in a polyethylene sealant cartridge (capacity 330 mL) and sealed with an inner stopper. The cartridge was stored in a dryer at 70°C for 7 days, then removed and the tack-free time was measured in the same manner as above. If the tack-free time was within twice the tack-free time of each composition immediately after preparation, it was evaluated as ○ (pass), and if it took more than twice the time, it was evaluated as × (fail). The results are shown in Table 1.

[0084] [Table 1]

[0085] The results in Table 1 reveal that in Examples 1 to 3, the compositions were easier to prepare than in Comparative Examples 1 to 3, and the storage stability was also good.

[0086] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. (A) (A1) 100 parts by mass of an organopolysiloxane having both molecular chain terminals capped with silanol groups and / or an organopolysiloxane having one molecular chain terminal capped with a silanol group, and (A2) An organosilicon compound represented by the following general formula (1): 0.01 to 30 parts by mass 【Chemical 1】 (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms; R 2 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms; R 3 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, a is an integer of 1 to 3, b is 1 or 2, and a+b is an integer of 2 to 4. a reaction mixture comprising an organopolysiloxane (A1), in which silanol groups at the molecular chain terminals of the organopolysiloxane (A2) are blocked with hydrolyzable organosilyl groups derived from the organosilicon compound (A2) and represented by the following formula: 【Chemistry 2】 (In the formula, R 1 , R 2 , R 3 , a, b are the same as above.) (B) 0.01 to 30 parts by mass of a hydrolyzable organosilane compound represented by the following general formula (2) and / or a partial hydrolysis condensate thereof (excluding component (A2)), and R 4 4-c Si(OR 5 ) c (2) (In the formula, R 4 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 5 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and c is 3 or 4. (C) Curing catalyst: 0.001 to 20 parts by mass A room-temperature-curable organopolysiloxane composition comprising:

2. Furthermore, per 100 parts by mass of the component (A1), (D) Isocyanate compound: 0.01 to 10 parts by mass, (E) silylating agent: 0.01 to 10 parts by mass, (F) Filler: 1 to 1,000 parts by mass, (G) adhesion promoter (excluding components (A2), (B), (C), and (D)): 0.1 to 30 parts by mass, and (H) Plasticizer: 1 to 1,000 parts by mass 2. The room-temperature-curable organopolysiloxane composition according to claim 1, which contains one or more compounds selected from the following:

3. 2. The room-temperature-curable organopolysiloxane composition according to claim 1, wherein component (A2) is a dehydrocondensation reaction product of a hydrolyzable (organo)hydrosilane compound and a diorganohydroxylamine compound.

4. 2. The room-temperature-curable organopolysiloxane composition according to claim 1, wherein component (A1) is a diorganopolysiloxane represented by the following general formula (3) in which both molecular chain terminals are capped with silanol groups and / or a diorganopolysiloxane represented by the following general formula (4) in which one molecular chain terminal is capped with a silanol group: 【Chemistry 3】 (In the formula, R 6 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, A is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, and k is an integer that provides a viscosity of the diorganopolysiloxane at 23°C of 100 to 1,000,000 mPa·s. 【Chemistry 4】 (In the formula, R 6 , A is the same as in formula (3), and m is an integer that gives the diorganopolysiloxane a viscosity of 100 to 1,000,000 mPa·s at 23°C.

5. (A) (A1) 100 parts by mass of an organopolysiloxane having both molecular chain terminals capped with silanol groups and / or an organopolysiloxane having one molecular chain terminal capped with a silanol group, and (A2) An organosilicon compound represented by the following general formula (1): 0.01 to 30 parts by mass 【Chemistry 5】 (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms; R 2 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms; R 3 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, a is an integer of 1 to 3, b is 1 or 2, and a+b is an integer of 2 to 4. a reaction mixture comprising an organopolysiloxane (A1), in which silanol groups at the molecular chain terminals of the organopolysiloxane (A2) are blocked with hydrolyzable organosilyl groups derived from the organosilicon compound (A2) and represented by the following formula: 【Chemistry 6】 (In the formula, R 1 , R 2 , R 3 , a, b are the same as above.) (B) 0.01 to 30 parts by mass of a hydrolyzable organosilane compound represented by the following general formula (2) and / or a partial hydrolysis condensate thereof (excluding component (A2)), and R 4 4-c Si(OR 5 ) c (2) (In the formula, R 4 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 5 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and c is 3 or 4. (C) Curing catalyst: 0.001 to 20 parts by mass A method for producing a room-temperature-curable organopolysiloxane composition comprising: [i]: a step of uniformly mixing the component (A1), the component (A2), and a part or all of the component (B) (provided that the component (C) is not included in the step [i]); and [ii]: A step of blending the remainder of component (B) and component (C) into the mixture. A method for producing a room-temperature-curable organopolysiloxane composition comprising:

6. 6. The method for producing a room-temperature-curable organopolysiloxane composition according to claim 5, wherein step [i] produces a reaction mixture (A) containing an organopolysiloxane in which silanol groups at the molecular chain terminals of the organopolysiloxane in component (A1) have been blocked with hydrolyzable organosilyl groups derived from the organosilicon compound in component (A2) and represented by the following formula: 【Chemistry 7】 (In the formula, R 1 , R 2 , R 3 , a, b are the same as above.)

7. 6. The method for producing a room-temperature-curable organopolysiloxane composition according to claim 5, wherein 10 to 100% by mass of the total component (B) is blended in step [i], and 0 to 90% by mass of the total component (B) is blended in step [ii].

8. Furthermore, per 100 parts by mass of the component (A1), (D) Isocyanate compound: 0.01 to 10 parts by mass, (E) silylating agent: 0.01 to 10 parts by mass, (F) Filler: 1 to 1,000 parts by mass, (G) adhesion promoter (excluding components (A2), (B), (C), and (D)): 0.1 to 30 parts by mass, and (H) Plasticizer: 1 to 1,000 parts by mass 6. The method for producing a room-temperature-curable organopolysiloxane composition according to claim 5, wherein one or more selected from the group consisting of:

9. 6. The method for producing a room-temperature-curable organopolysiloxane composition according to claim 5, wherein component (A2) is a dehydrocondensation reaction product of a hydrolyzable (organo)hydrosilane compound and a diorganohydroxylamine compound.

10. 6. The method for producing a room-temperature-curable organopolysiloxane composition according to claim 5, wherein component (A1) is a diorganopolysiloxane represented by the following general formula (3) in which both molecular chain terminals are capped with silanol groups and / or a diorganopolysiloxane represented by the following general formula (4) in which one molecular chain terminal is capped with a silanol group: 【Chemistry 8】 (In the formula, R 6 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, A is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, and k is an integer that provides a viscosity of the diorganopolysiloxane at 23°C of 100 to 1,000,000 mPa·s. 【Chemistry 9】 (In the formula, R 6 , A is the same as in formula (3), and m is an integer that gives the diorganopolysiloxane a viscosity of 100 to 1,000,000 mPa·s at 23°C.

11. A coating agent comprising the room-temperature-curable organopolysiloxane composition according to any one of claims 1 to 4.

12. An adhesive comprising the room-temperature-curable organopolysiloxane composition according to any one of claims 1 to 4.

13. A sealant comprising the room-temperature-curable organopolysiloxane composition according to any one of claims 1 to 4.

14. An article having a coating layer comprising a cured product of the room-temperature-curable organopolysiloxane composition according to any one of claims 1 to 4.

15. An article bonded and / or sealed with a cured product of the room temperature curable organopolysiloxane composition according to any one of claims 1 to 4.

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