Room-temperature-curable organopolysiloxane composition and method for producing same

Abstract

To provide a method for producing a room temperature-curable organopolysiloxane composition which is excellent in storage stability without thickening or gelling during preparation, is cured at room temperature by moisture (water) in the atmosphere, and can inexpensively and easily obtain a cured product in which discoloration after high temperature heating is suppressed, and to provide the composition.SOLUTION: [I] A silicone resin composition comprising (A-1) an organopolysiloxane capped at both ends of the molecular chain with SiOH groups and having a specific viscosity, (a- 2) a hydrolyzable organosilane compound having a specific structure and / or a partial hydrolytic condensate thereof, and (a- 3) a compound having one amino group, A method for preparing a RTC organopolysiloxane composition, comprising the steps of mixing an aromatic ring-free silane coupling agent and / or a partial hydrolytic condensate thereof at room temperature, allowing the mixture to stand in a moisture-free environment for at least 6 hours for reaction to form a reaction product mixture (A), and mixing components (A), (B) and (C) to homogeneity.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a room-temperature-curable organopolysiloxane composition that cures in the presence of atmospheric moisture (water) at room temperature (5°C or higher but lower than 40°C, particularly 23°C ± 15°C) to give a cured silicone rubber (silicone elastomer elastic material), and to a method for producing the same. In particular, the present invention relates to a dealcohol-type organopolysiloxane composition that can suppress or eliminate a sudden increase in viscosity or gelation during preparation, reduces yellowing of the cured rubber, and has excellent storage stability in a sealed container, and a method for producing the same. [Background technology]

[0002] Among the organopolysiloxane compositions that have hitherto been developed to cure at room temperature to form a rubber-like elastomer, so-called one-component (single-liquid) room-temperature-curable organopolysiloxane compositions, in which the curing reaction proceeds upon contact with moisture in the air, do not require the user to weigh out and mix the base composition (a mixture containing a base polymer, filler, curing catalyst, etc.) and curing agent composition (a mixture containing a crosslinking agent, etc.) according to the blending ratio just before use, as is the case with two-component compositions, and are therefore free from the tedious process of blending errors.Furthermore, these compositions generally exhibit excellent adhesion to a wide range of substrates, even when a primer is not used to improve adhesion, and are therefore widely used as elastic adhesives, sealants, and coating materials in the electrical and electronics industries, as well as in building and civil engineering sealants and coating materials.

[0003] These one-component, room-temperature-curable organopolysiloxane compositions are classified as condensation-cure types based on the reaction mechanism, and further classified by the compounds released from the composition upon contact with moisture in the air. Representative examples include deacetylated, deoximed, deamidated, dehydroxylamine, deacetone-cure, and dealcohol-cure organopolysiloxane compositions. Deacetylated types release acetic acid during the curing reaction, which often causes a problem with its strong acetic acid odor. Furthermore, their corrosive nature limits their applications, limiting their use in Japan to a few applications, such as small ornamental aquariums. Deoximed types are the most widely used in Japan for commercial and consumer applications due to their ease of production, reduced odor compared to deacetylated types, non-corrosion to metals, and the inclusion of a silane coupling agent allows for compositions with adhesive properties to a wide range of substrates. However, in recent years, concerns have grown over the carcinogenicity of methyl ethyl ketoxime, an oxime compound generated and released during curing, and the European Chemical Safety Laboratory (ECL) upgraded the carcinogenicity classification of methyl ethyl ketoxime to Category 1b in March 2022. While it can be used in factories equipped with local exhaust ventilation systems and with adequate safety precautions, it is considered difficult for ordinary consumers to comply with the cumbersome precautions when using it casually as a DIY project, rather than as a commercial product for professional use. Alternatives to oxime-free compounds that generate and cure methyl isobutyl ketoxime or methyl propyl ketoxime have also been proposed, but the former has a strong odor and requires the installation of local exhaust ventilation systems at the point of use, and the latter remains extremely expensive for industrial use. The deamidated and dehydroxylamine types use amide silanes and aminoxy silanes as crosslinking agents, while the deacetone type uses isopropenoxy silanes as crosslinking agents, which are expensive. Although they exhibit good properties for specific applications, they are still too expensive for general-purpose use by the general consumer and are not widely used.

[0004] On the other hand, dealcohol-reducing organopolysiloxane compositions, which cure by releasing alcohol during curing, have advantages such as less odor, are not corrosive to metals such as copper and iron, and by incorporating a silane coupling agent, compositions with excellent self-adhesion (adhesion to various substrates after curing when no primer is used) can be obtained, as well as excellent adhesive durability. Therefore, dealcohol-reducing organopolysiloxane compositions can be said to be a curing type that is easier for the average consumer to use than oxime-type compositions.

[0005] However, compared with the other curing types mentioned above, it is extremely difficult to inexpensively produce one-component, dealcohol-free organopolysiloxane compositions. One reason for this is the low condensation reactivity of alkoxysilanes with silanol groups. This leads to two major drawbacks. First, as with the production of other curing types, when a polydimethylsiloxane with both terminals capped with silanol groups is used as the starting material, methyltrimethoxysilane is added as a crosslinking agent, and an organotitanium compound or organotin compound is added as a catalyst, a sudden increase in viscosity occurs during production, and gelation occurs if the amount of crosslinking agent added is insufficient. This viscosity increase and gelation significantly reduce the production efficiency of the organopolysiloxane composition and, in the worst case, can lead to production failure. To solve this problem, an excess of crosslinking agent must be added to cap the terminal silanol groups of the organopolysiloxane with alkoxysilyl groups. Excess crosslinking agent impairs the deep curing properties of room-temperature-curable organopolysiloxane compositions, preventing practical performance. For these reasons, it is difficult to obtain room-temperature-curable organopolysiloxane compositions with higher performance than other curing types, especially oxime-free types. Second, even if performance can be ensured, there is a drawback in storage stability; while performance can be maintained for a short period after production, the properties immediately after production are lost over time during storage. Furthermore, after storage in a high-temperature environment exceeding 50°C, which is often the case when the composition is stored in direct sunlight at the site of use or in a container during transport, not only are the properties immediately after production lost even after a relatively short period of storage, but poor curing can also occur.

[0006] One-component, dealcohol-removing organopolysiloxane compositions have long been proposed, and a representative example of such a composition is a composition proposed in Japanese Patent Publication No. 39-27643 (Patent Document 1) that comprises a terminally silanol-blocked organopolysiloxane, an alkoxysilane, and a titanium compound. In addition, Japanese Patent Publication No. 55-43119 (Patent Document 2) proposes a composition that comprises an organopolysiloxane having alkoxysiloxy groups at its terminals, an alkoxysilane, and an alkoxytitanium. However, these compositions suffer from problems such as a lack of storage stability when calcium carbonate is added to impart good physical properties to the sealant, resulting in a failure to achieve the desired properties when the composition is used after long-term storage, or a failure to cure when stored in a high-temperature environment exceeding 50°C. Furthermore, no inexpensive method for preparing organopolysiloxanes having alkoxysiloxy groups has been disclosed. Furthermore, Japanese Patent Publication No. 7-39547 (Patent Document 3) proposes a composition that exhibits excellent storage stability in a sealed state. However, the composition proposed therein requires the use of a base polymer in which an alkoxysilyl alkylene group is modified at the end of an organopolysiloxane, and problems arise, such as high industrial costs for the preparation of this polymer. The present inventors proposed in Japanese Patent Publication No. 4775600 (Patent Document 4) that storage stability can be improved by incorporating a fatty acid ester of a polyhydric alcohol. However, the problem of thickening that occurs when preparing a room-temperature-curable organopolysiloxane composition using an organopolysiloxane terminally blocked with silanol groups remains unresolved.

[0007] As described above, in order to obtain a dealcohol-removing organopolysiloxane composition, there are two ways to do it: either use an organopolysiloxane that has been terminally blocked with alkoxysilyl groups as the base polymer, or 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. However, in order to achieve ease of production without thickening or gelation during preparation and storage stability, it is most preferable to use an organopolysiloxane that has been terminally blocked with alkoxysilyl groups as the base polymer. However, this method has the disadvantages of being expensive, requiring a long time to remove the catalyst after terminal blocking, which increases costs. For this reason, a commonly known method for end-capping silanol groups during the manufacturing process involves incorporating a basic silane compound, such as an amino group-containing silane, as an end-capping catalyst, and Japanese Patent Publication No. 5888112 (Patent Document 5) and Japanese Patent Publication No. 6252466 (Patent Document 6) 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, there are still problems that make it economically disadvantageous. Furthermore, on fluororesin-coated aluminum surfaces, which are difficult to bond to, these catalyst components act as adhesion inhibitors, significantly delaying the onset of adhesion in low-temperature environments below 10°C, or even if adhesion does occur, sufficient adhesion cannot be achieved after exposure to harsh conditions such as immersion in hot water.

[0008] In order to solve these problems, the present inventors proposed in Japanese Patent Laid-Open Publication No. 2023-086691 (Patent Document 7) a method for inexpensively producing a room-temperature-curable organopolysiloxane composition using fumed silica as a filler, and the room-temperature-curable organopolysiloxane composition. However, problems arose, such as yellowing at high temperatures such as 90°C compared to conventional oxime-free types, and poor curing when applied to compositions using titanium-catalyzed calcium carbonate as a filler. Thus, it was difficult to inexpensively obtain a room-temperature-curable organopolysiloxane composition that could be used effectively under a variety of conditions. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Special Publication No. 39-27643 [Patent Document 2] Japanese Patent Application Publication No. 55-43119 [Patent Document 3] Special Publication No. 7-39547 [Patent Document 4] Patent No. 4775600 [Patent Document 5] Patent No. 6252466 [Patent Document 6] Patent No. 5888112 [Patent Document 7] Japanese Patent Application Publication No. 2023-086691 Summary of the Invention [Problem to be solved by the invention]

[0010] The object of the present invention is to solve the problems of the prior art described above and to provide a dealcohol-type room-temperature-curable organopolysiloxane composition that cures at room temperature in the presence of atmospheric moisture to give a cured silicone rubber product, and in particular to provide a method for producing a room-temperature-curable organopolysiloxane composition that can easily produce a room-temperature-curable organopolysiloxane composition that has excellent storage stability even when packaged in a sealed state, and to provide said room-temperature-curable organopolysiloxane composition. [Means for solving the problem]

[0011] As a result of extensive research into achieving the above object, the present inventors have found that [I]: (A-1) The following general formula (1) [ka] (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and m is an integer of 10 or greater. 100 parts by mass of an organopolysiloxane represented by the formula (I) having both molecular chain terminals blocked with silanol groups and a viscosity at 23°C of 20 to 1,000,000 mPa s, (A-2) The following general formula (2) [ka] (In the formula, R 2 is a vinyl group, and R 3 are independently unsubstituted monovalent hydrocarbon groups having 1 to 3 carbon atoms, and a is 3 or 4. and / or a partial hydrolysis condensate thereof: 0.2 to 10 parts by mass, (A-3) The following general formula (3) [ka] (In the formula, R 5 is an aliphatic divalent hydrocarbon group having 1 to 10 carbon atoms, and R 6 and R 7 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and b is 2 or 3. and / or a partial hydrolysis condensate thereof: 0.1 to 5 parts by mass uniformly mixed at room temperature (5°C or higher but lower than 40°C), and then allowed to stand for reaction at room temperature in a moisture-blocking environment for 6 hours or more to obtain a reaction product mixture (A); [II]: The reaction product mixture (A) is The component (A-2): 0 to 8 parts by mass (however, the total amount of the components in steps [I] and [II] is 0.2 to 10 parts by mass per 100 parts by mass of the component (A-1)), The above-mentioned (A-3) component: 0 to 4 parts by mass (however, the total amount of the (A-3) component in steps [I] and [II] is 0.1 to 5 parts by mass per 100 parts by mass of the (A-1) component), (B) Curing catalyst: 0.001 to 20 parts by mass, and (C) Inorganic filler: 5 to 300 parts by mass A process of blending and mixing the above ingredients evenly The present inventors have found that a room-temperature-curable organopolysiloxane composition obtained by a method for producing a room-temperature-curable organopolysiloxane composition comprising the compound (I) does not thicken or gel during preparation, has excellent storage stability in a sealed container, cures in the presence of atmospheric moisture (water) at room temperature (5°C or higher and lower than 40°C, particularly 23°C ± 15°C), and produces a cured product that is inhibited from discoloring after high-temperature heating, at low cost and in a simple manner, leading to the completion of the present invention.

[0012] Accordingly, the present invention provides the following method for producing a room-temperature-curable organopolysiloxane composition and the room-temperature-curable organopolysiloxane composition. [1] [I]: (A-1) The following general formula (1) [ka] (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and m is an integer of 10 or greater. 100 parts by mass of an organopolysiloxane represented by the formula (I) having both molecular chain terminals blocked with silanol groups and a viscosity at 23°C of 20 to 1,000,000 mPa s, (A-2) The following general formula (2) [ka] (In the formula, R 2 is a vinyl group, and R 3 are independently unsubstituted monovalent hydrocarbon groups having 1 to 3 carbon atoms, and a is 3 or 4. and / or a partial hydrolysis condensate thereof: 0.2 to 10 parts by mass, (A-3) The following general formula (3) [ka] (In the formula, R 5 is an aliphatic divalent hydrocarbon group having 1 to 10 carbon atoms, and R 6 and R 7 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and b is 2 or 3. and / or a partial hydrolysis condensate thereof: 0.1 to 5 parts by mass uniformly mixed at room temperature (5°C or higher but lower than 40°C), and then allowed to stand for reaction at room temperature in a moisture-blocking environment for 6 hours or more to obtain a reaction product mixture (A); [II]: The reaction product mixture (A) is The component (A-2): 0 to 8 parts by mass (however, the total amount of the components in steps [I] and [II] is 0.2 to 10 parts by mass per 100 parts by mass of the component (A-1)), The above-mentioned (A-3) component: 0 to 4 parts by mass (however, the total amount of the (A-3) component in steps [I] and [II] is 0.1 to 5 parts by mass per 100 parts by mass of the (A-1) component), (B) Curing catalyst: 0.001 to 20 parts by mass, and (C) Inorganic filler: 5 to 300 parts by mass A process of blending and mixing the above ingredients evenly A method for producing a room-temperature-curable organopolysiloxane composition comprising: [2] In the above step [I] and / or step [II], (A-4) The following general formula (4) [ka] (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and m is an integer of 10 or greater. an organopolysiloxane represented by the formula (I) having one end blocked with a silanol group and the other end blocked with a triorganosilyl group and having a viscosity at 23°C of 20 to 1,000,000 mPa s: 0.1 to 100 parts by mass in total per 100 parts by mass of component (A-1) in steps [I] and [II] A method for producing the room-temperature-curable organopolysiloxane composition according to [1], comprising: [3] In the above step [I] and / or step [II], (A-5) The following general formula (5) [ka] (In the formula, R 4 is an aliphatic divalent hydrocarbon group having 2 to 10 carbon atoms, and R 5 is an aliphatic divalent hydrocarbon group having 1 to 10 carbon atoms, and R 6 and R 7 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and b is 2 or 3. and / or a partial hydrolysis condensate thereof: 0.1 to 5 parts by mass in total in step [I] and step [II] per 100 parts by mass of component (A-1). A method for producing the room-temperature-curable organopolysiloxane composition according to [1] or [2], comprising: [4] (A-1) The following general formula (1) [ka] (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and m is an integer of 10 or greater. 100 parts by mass of an organopolysiloxane represented by the formula (I) having both molecular chain terminals blocked with silanol groups and a viscosity at 23°C of 20 to 1,000,000 mPa s, (A-2) The following general formula (2) [ka] (In the formula, R 2is a vinyl group, and R 3 are independently unsubstituted monovalent hydrocarbon groups having 1 to 3 carbon atoms, and a is 3 or 4. and / or a partial hydrolysis condensate thereof: 0.2 to 10 parts by mass, (A-3) The following general formula (3) [ka] (In the formula, R 5 is an aliphatic divalent hydrocarbon group having 1 to 10 carbon atoms, and R 6 and R 7 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and b is 2 or 3. and / or a partial hydrolysis condensate thereof: 0.1 to 5 parts by mass A reaction product mixture (A) obtained by allowing the mixture having the above blending ratio to react at room temperature in a moisture-blocking environment for 6 hours or more. The component (A-2): 0 to 8 parts by mass (however, 0.2 to 10 parts by mass per 100 parts by mass of the component (A-1) in the entire composition), The component (A-3): 0 to 4 parts by mass (however, 0.1 to 5 parts by mass per 100 parts by mass of the component (A-1) in the entire composition), (B) Curing catalyst: 0.001 to 20 parts by mass, and (C) Inorganic filler: 5 to 300 parts by mass A room temperature curable organopolysiloxane composition comprising: [5] The reaction product mixture (A) further comprises: (A-4) The following general formula (4) [ka] (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and m is an integer of 10 or greater. an organopolysiloxane represented by the formula: The room-temperature-curable organopolysiloxane composition according to [4], which is obtained by reacting a mixture containing [6] The component (A-5) is a compound represented by the following general formula (5): [ka] (In the formula, R 4 is an aliphatic divalent hydrocarbon group having 2 to 10 carbon atoms, and R 5 is an aliphatic divalent hydrocarbon group having 1 to 10 carbon atoms, and R 6 and R 7 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and b is 2 or 3. and / or a partial hydrolysis condensate thereof in an amount of 0.1 to 5 parts by mass per 100 parts by mass of the component (A-1) in the following embodiment (i) and / or (ii): (i) The reaction product mixture (A) is obtained by further reacting a mixture containing component (A-5). (ii) A composition containing component (A-5) as the sole component. [7] Furthermore, in one molecule of (D), a compound represented by the following general formula (6) -OC(=O)CHR 8 (6) (In the formula, R 8 is a hydrogen atom or a monovalent hydrocarbon group. and β hydroxy groups (where α is an integer of 1 to 3, β is 0, 1, or 2, and α+β=3 is satisfied). : 0.1 to 5 parts by mass per 100 parts by mass of component (A-1) The room-temperature-curable organopolysiloxane composition according to any one of [4] to [6], comprising: [8] The room-temperature-curable organopolysiloxane composition according to [7], wherein component (D) is a fatty acid ester of a polyhydric alcohol having three hydroxy groups in one molecule and having a fatty acid ester residue represented by general formula (6): [9] The room-temperature-curable organopolysiloxane composition according to [7], wherein component (D) is a fatty acid ester of glycerin having a fatty acid ester residue represented by general formula (6).

[10] The room-temperature-curable organopolysiloxane composition according to [7], wherein component (D) is at least one selected from triacetin, diacetin, and monoacetin.

[11] Furthermore, (E) a silylating agent: 0.1 to 10 parts by mass per 100 parts by mass of the component (A-1) The room-temperature-curable organopolysiloxane composition according to any one of [4] to

[10] , comprising: [Effects of the Invention]

[0013] According to the method for producing a room-temperature-curable organopolysiloxane composition of the present invention, it is possible to easily and inexpensively provide a dealcohol-type room-temperature-curable organopolysiloxane composition that exhibits excellent storage stability when packaged in a sealed container and that gives a cured silicone rubber product that exhibits reduced discoloration after high-temperature heating, without causing thickening during preparation. DETAILED DESCRIPTION OF THE INVENTION

[0014] The method for producing the room-temperature-curable organopolysiloxane composition of the present invention comprises the steps of: [I]: (A-1) The following general formula (1) [ka] (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and m is an integer of 10 or greater. 100 parts by mass of an organopolysiloxane represented by the formula (I) having both molecular chain terminals blocked with silanol groups and a viscosity at 23°C of 20 to 1,000,000 mPa s, (A-2) The following general formula (2) [ka] (In the formula, R 2 is a vinyl group, and R 3 are independently unsubstituted monovalent hydrocarbon groups having 1 to 3 carbon atoms, and a is 3 or 4. and / or a partial hydrolysis condensate thereof: 0.2 to 10 parts by mass, (A-3) The following general formula (3) [ka] (In the formula, R 5 is an aliphatic divalent hydrocarbon group having 1 to 10 carbon atoms, and R 6 and R 7 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and b is 2 or 3. and / or a partial hydrolysis condensate thereof: 0.1 to 5 parts by mass uniformly mixed at room temperature (5°C or higher but lower than 40°C), and then allowed to stand for reaction at room temperature in a moisture-blocking environment for 6 hours or more to obtain a reaction product mixture (A); [II]: The reaction product mixture (A) is The component (A-2): 0 to 8 parts by mass (however, the total amount of the components in steps [I] and [II] is 0.2 to 10 parts by mass per 100 parts by mass of the component (A-1)), The above-mentioned (A-3) component: 0 to 4 parts by mass (however, the total amount of the (A-3) component in steps [I] and [II] is 0.1 to 5 parts by mass per 100 parts by mass of the (A-1) component), (B) Curing catalyst: 0.001 to 20 parts by mass, and (C) Inorganic filler: 5 to 300 parts by mass A process of blending and mixing the above ingredients evenly The compound comprises:

[0015] The room-temperature-curable organopolysiloxane composition obtained by the production method of the present invention has the following properties: (A) a reaction mixture obtained by allowing a mixture of the above components (A-1) to (A-3) in the above-mentioned mixing ratios to react at room temperature in a moisture-blocking environment for 6 hours or more; (B) curing catalyst; (C) inorganic fillers, and If necessary, it further contains specific amounts of the above-mentioned components (A-2) and (A-3).

[0016] Step [I] will be explained. Step [I] is a step for preparing component (A), which is the main component of the room-temperature-curable organopolysiloxane composition of the present invention. At least components (A-1), (A-2), and (A-3) described below are uniformly mixed at room temperature (5°C or higher but lower than 40°C) in the amounts described below, and then the mixture is left to react at room temperature in a moisture-blocking environment for 6 hours or longer to obtain reaction product mixture (A).

[0017] [Component (A-1)] Component (A-1) is an organopolysiloxane represented by the following general formula (1), in which both molecular chain terminals are blocked with silanol groups (hydroxyl groups bonded to silicon atoms), and which has a viscosity at 23°C of 20 to 1,000,000 mPa·s: [ka] (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and m is an integer of 10 or greater.

[0018] In the formula, R 1are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, such as alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, and decyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl and tolyl; and groups in which the hydrogen atoms of these groups are partially substituted with halogen atoms or the like, such as 3,3,3-trifluoropropyl. Of these, methyl, phenyl, and 3,3,3-trifluoropropyl are preferred, with methyl being particularly preferred. 1 may be the same group or different groups.

[0019] Furthermore, m is an integer of 10 or greater that provides a viscosity of the organopolysiloxane at 23°C in the range of 20 to 1,000,000 mPa·s, preferably 500 to 100,000 mPa·s, and is typically an integer of 10 to 3,000, preferably 20 to 2,000, and more preferably 30 to 1,200. If m is less than 10, the viscosity of the composition of the present invention will be too low, impairing workability and failing to provide elastic followability after curing.

[0020] Component (A-1) has a viscosity at 23°C of 20 to 1,000,000 mPa·s, preferably 500 to 100,000 mPa·s. If the viscosity is less than 20 mPa·s, not only will the workability of the composition of the present invention be impaired, but elastic followability after curing will also be impaired. If the viscosity exceeds 1,000,000 mPa·s, the viscosity will be too high, making production of the composition itself difficult and significantly reducing workability. Viscosity can be measured using a rotational viscometer (e.g., BL type, BH type, BS type, cone-plate type, rheometer, etc.) (the same applies hereinafter).

[0021] The component (A-1) may be used alone or in combination of two or more types. It is preferable that the entire component (A-1) is blended in step [I].

[0022] [Component (A-2)] Component (A-2) is a hydrolyzable organosilane compound such as an alkoxysilane represented by the following general formula (2) and / or a partial hydrolysis condensate thereof, and acts as an end-blocking agent for component (A-1), a crosslinking agent (curing agent) for the composition, and a dehydrating agent. [ka] (In the formula, R 2 is a vinyl group, and R 3 are independently unsubstituted monovalent hydrocarbon groups having 1 to 3 carbon atoms, and a is 3 or 4.

[0023] In the formula, R 2 is a vinyl group. R 3 are independently unsubstituted monovalent hydrocarbon groups having 1 to 3 carbon atoms, and examples thereof include alkyl groups such as methyl, ethyl, propyl, and isopropyl. Methyl and ethyl groups are preferred, and methyl is particularly preferred. 3 may be the same or different. Also, a is 3 or 4.

[0024] Examples of the hydrolyzable organosilane compound of component (A-2) include tetramethoxysilane, vinyltrimethoxysilane, tetraethoxysilane, vinyltriethoxysilane, tetrapropoxysilane, vinyltripropoxysilane, tetraisopropoxysilane, and vinyltriisopropoxysilane. In the present invention, the term "partially hydrolyzed condensate" refers to an organosiloxane oligomer having at least two, and preferably three or more, residual hydrolyzable groups such as alkoxy groups in the molecule, which is produced by partial hydrolysis and condensation of the hydrolyzable organosilane compound (the same applies hereinafter).

[0025] In the present invention, the hydrolyzable organosilane compound and / or its partial hydrolysis condensate of component (A-2) is preferably vinyltrimethoxysilane, vinyltriethoxysilane, or their partial hydrolysis condensates, which can be obtained industrially at relatively low cost. The component (A-2) may be used alone or in combination of two or more types.

[0026] The amount of component (A-2) blended is 0.2 to 10 parts by mass, and preferably 0.2 to 8 parts by mass, per 100 parts by mass of component (A-1). If the blending amount is too small, the endblocking rate will be poor, making it impossible to produce a room-temperature-curable organopolysiloxane composition. If the blending amount is too large, the curing rate of the room-temperature-curable organopolysiloxane composition will be slow, resulting in poor mechanical properties after curing and also being economically disadvantageous. Note that component (A-2) functions as an end-blocking agent for component (A-1) and also as a crosslinking agent (curing agent) for the composition. Therefore, in the production method of the present invention, the entire component (A-2) (100 mass%) may be blended in step [I], or a portion of component (A-2) (for example, 90 to 10 mass%, particularly 75 to 25 mass%) may be blended in step [I], and the remainder of component (A-2) (for example, 10 to 90 mass%, particularly 25 to 75 mass%) may be blended in step [II].

[0027] [Component (A-3)] Component (A-3) is an amino-functional silane coupling agent and / or a partial hydrolysis condensate thereof, which has an amino group (one primary amino group) per molecule and does not contain any aromatic rings, and is represented by the following general formula (3). Component (A-3) exerts important effects as an end-blocking catalyst (condensation catalyst) for component (A-1), an end-blocking agent for component (A-1), and an adhesion promoter that imparts adhesion to the room-temperature-curable organopolysiloxane composition of the present invention. [ka] (In the formula, R 5 is an aliphatic divalent hydrocarbon group having 1 to 10 carbon atoms, and R 6 and R7 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and b is 2 or 3.

[0028] In the formula, R 5 is an aliphatic divalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include alkylene groups such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), pentamethylene, hexamethylene, heptamethylene, and octamethylene. Of these, trimethylene and octamethylene are preferred.

[0029] Also, in the formula, R 6 and R 7 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, and decyl, cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl, alkenyl groups such as vinyl and allyl, aryl groups such as phenyl and tolyl, and groups in which the hydrogen atoms of these groups are partially substituted with halogen atoms, such as 3,3,3-trifluoropropyl. Of these, methyl and ethyl groups are preferred. Also, b is 2 or 3.

[0030] The silane coupling agent and / or its partial hydrolysis condensate of component (A-3) does not contain an aromatic ring or, preferably, a conjugated aliphatic unsaturated double bond in its molecular structure. If a compound and / or its hydrolysis condensate containing such a ring is used, the cured silicone rubber will yellow after exposure to ultraviolet light, making it unsuitable for outdoor sealing applications or indoor sealing applications exposed to germicidal lamp light.

[0031] Examples of the component (A-3) include 3-aminopropyltrimethoxysilane, 8-aminooctyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 8-aminooctyltriethoxysilane, and partial hydrolysis condensates thereof, with 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and / or partial hydrolysis condensates thereof being preferred due to their low cost and high effectiveness. The component (A-3) may be used alone or in combination of two or more types.

[0032] The amount of component (A-3) blended is 0.1 to 5 parts by mass, and preferably 0.2 to 4 parts by mass, per 100 parts by mass of component (A-1). Less than 0.1 part by mass will not provide sufficient adhesion, while more than 5 parts by mass will not only be cost-effective but may also result in discoloration after curing. The component (A-3) not only acts as a catalyst and / or blocking agent for the blocking reaction of the terminal silanol groups of the component (A-1) in step [I], but also as a component (adhesion-imparting agent) that imparts adhesion to the cured product (silicone rubber cured product) obtained from the composition of the present invention. Therefore, in the production method of the present invention, the entire component (A-3) (100% by mass) may be blended in step [I], or a portion of the component (A-3) (for example, 90 to 10% by mass, particularly 75 to 25% by mass) may be blended in step [I], and the remainder of the component (A-3) (for example, 10 to 90% by mass, particularly 25 to 75% by mass) may be blended in step [II].

[0033] [Component (A-4)] The room-temperature-curable organopolysiloxane composition of the present invention may further contain, as an optional component (A-4), an organopolysiloxane represented by the following general formula (4), in which one end is capped with a silanol group (a hydroxyl group bonded to a silicon atom) and the other end is capped with a triorganosilyl group, and which has a viscosity at 23°C of 20 to 1,000,000 mPa s: [ka] (In the formula, R 1 , m is the same as above.)

[0034] By incorporating component (A-4), it is possible to obtain a room-temperature-curable organopolysiloxane composition that exhibits little wall thinning, good workability, and gives a cured product with excellent adhesiveness, particularly when used for butt joints of porous cut surfaces such as calcium silicate boards.

[0035] In the formula, R 1 , m is R in Eq. (1) 1 , m, and the same examples as above can be given.

[0036] The viscosity of component (A-4) at 23°C is 20 to 1,000,000 mPa·s, and preferably 500 to 100,000 mPa·s. If the viscosity is less than 20 mPa·s, the desired effect of addition may not be achieved, while if it exceeds 1,000,000 mPa·s, the viscosity of the composition may become too high, impairing workability.

[0037] The component (A-4) may be used alone or in combination of two or more.

[0038] When component (A-4) is added, the amount added is 0.1 to 100 parts by mass, and preferably 1 to 90 parts by mass, per 100 parts by mass of component (A-1). Less than 0.1 part by mass will not reduce the cured rubber's elastic modulus, while more than 100 parts by mass will reduce curability or will not reduce wall thinning.

[0039] When the component (A-4) is blended, it can be blended in either step [I] and / or step [II], but it is preferable to blend it in step [I] at the same time as the component (A-1).

[0040] [Component (A-5)] The room-temperature-curable organopolysiloxane composition of the present invention may further contain, as an optional component, component (A-5), an amino-functional silane coupling agent and / or a partial hydrolysis condensate thereof, which has two amino groups (one primary amino group and one secondary amino group (imino group)) per molecule and does not contain an aromatic ring, as represented by the following general formula (5): The incorporation of component (A-5) has the effect of improving adhesion to a wide range of substrates. [ka] (In the formula, R 4 is an aliphatic divalent hydrocarbon group having 2 to 10 carbon atoms, and R 5 is an aliphatic divalent hydrocarbon group having 1 to 10 carbon atoms, and R 6 and R 7 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and b is 2 or 3.

[0041] In the formula, R 4 is an aliphatic divalent hydrocarbon group having 2 to 10 carbon atoms, and examples thereof include alkylene groups such as ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), pentamethylene, hexamethylene, heptamethylene, and octamethylene. Of these, ethylene, trimethylene, and octamethylene are preferred. Also, in the formula, R 5 , R 6 , R 7 and b is R in Equation (3) 5 , R 6 , R 7 and b, and examples thereof include those similar to those mentioned above. 5 is preferably a methylene group or a trimethylene group, and R 6 , R 7 As R, a methyl group or an ethyl group is preferred. 5 , R 6 , R 7 and b may be the same as or different from those in formula (3).

[0042] For the same reasons as for the component (A-3), the silane coupling agent and / or partial hydrolysis condensate thereof of the component (A-5) does not contain an aromatic ring or preferably a conjugated aliphatic unsaturated double bond in its molecular structure.

[0043] Examples of the component (A-5) include 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(3-aminopropylamino)propyltrimethoxysilane, 3-(8-aminooctylamino)propyltrimethoxysilane, [(2-aminoethylamino)methyl]trimethoxysilane, [(2-aminoethylamino)methyl]methyldimethoxysilane, and partial hydrolysis condensates thereof, with 3-(2-aminoethylamino)propyltrimethoxysilane and / or its partial hydrolysis condensates being preferred due to their low cost and high effectiveness. The component (A-5) may be used alone or in combination of two or more types.

[0044] The blend amount of component (A-5) is 0 to 5 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.15 to 4 parts by mass, per 100 parts by mass of component (A-1). Blending component (A-5) within this range improves adhesiveness after curing, but an amount exceeding 5 parts by mass is not only uneconomical but may also result in discoloration after curing. When component (A-5) is blended, the combined blend amount of components (A-5) and (A-3) is preferably 0.1 to 5 parts by mass per 100 parts by mass of component (A-1). When component (A-5) is further blended, the combined blend amount of components (A-3) and (A-5) is preferably 1 to 80% by mass, particularly 1 to 50% by mass, and even more preferably 1 to 45% by mass. When the (A-5) component is blended, it may be blended in step [I] or in step [II]. The entire (100% by mass) of the (A-5) component may be blended in step [I] or in step [II]. Alternatively, a portion of the (A-5) component (for example, 90 to 10% by mass, particularly 75 to 25% by mass) may be blended in step [I], and the remainder of the (A-5) component (for example, 10 to 90% by mass, particularly 25 to 75% by mass) may be blended in step [II].

[0045] When the component (A-5) is blended in step [I], it is preferable that the amount of the component (A-3) blended is greater than the amount of the component (A-5) blended.

[0046] When the (A-5) component is added in step [II], the total amount of the (A-5) component and the (A-3) component in step [II] is preferably 0.01 to 4 parts by mass per 100 parts by mass of the (A-1) component. Furthermore, the total amount of the (A-5) component and the (A-3) component in steps [I] and [II] is preferably 0.1 to 5 parts by mass per 100 parts by mass of the (A-1) component. When the components (A-3) and (A-5) are blended in step [II], it is preferable that the amount of the component (A-3) blended is greater than the amount of the component (A-5) blended.

[0047] [Component (A-6)] The room-temperature-curable organopolysiloxane composition of the present invention can further contain, as an optional component, component (A-6), a hydrolyzable organosilane compound other than component (A-2) and / or a partial hydrolysis condensate thereof. By incorporating component (A-6), it is possible to obtain the effect of adjusting the depth curability and physical properties after curing to desired performance.

[0048] Specific examples of the component (A-6) include (organo)alkoxysilane compounds that do not have a vinyl group, such as methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, isobutyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, and decyltrimethoxysilane, as well as their partial hydrolysis condensates; and bissilyl silane compounds, such as 1,2-bis(trimethoxysilyl)ethane, 1,6-bis(trimethoxysilyl)hexane, and 1,8-bis(trimethoxysilyl)octane, as well as their partial hydrolysis condensates. The component (A-6) may be used alone or in combination of two or more types.

[0049] The amount of component (A-6) blended is 0 to 10 parts by mass, preferably 0 to 5 parts by mass, per 100 parts by mass of component (A-1). When component (A-6) is blended, the amount is preferably 0.2 parts by mass or more per 100 parts by mass of component (A-1). If the blending amount is too small, the effect of addition may not be fully exerted, while if the blending amount is too large, deep curing may be slow or the rubber properties after curing may deteriorate. Furthermore, when component (A-6) is blended, the total amount of component (A-2) and component (A-6) blended is preferably 1 to 20 parts by mass per 100 parts by mass of component (A-1). Furthermore, when component (A-6) is blended, the total amount of component (A-2) and component (A-6) blended is preferably 10 to 90% by mass, particularly 20 to 80% by mass. When the (A-6) component is blended, the entire component (100% by mass) may be blended in step [I], or a portion of the (A-6) component (for example, 90 to 10% by mass, particularly 75 to 25% by mass) may be blended in step [I], and the remainder of the (A-6) component (for example, 10 to 90% by mass, particularly 25 to 75% by mass) may be blended in step [II].

[0050] The reaction mixture of component (A) can be obtained by uniformly mixing the components (A-1), (A-2), and (A-3), and, if necessary, other components, in the specified ratios at room temperature (5°C or higher but lower than 40°C), and then allowing the mixture to react at room temperature (5°C or higher but lower than 40°C) in a moisture-blocking environment for 6 hours or more.

[0051] The mixing operation of components (A-1), (A-2), (A-3), and, if necessary, other components, may be carried out in either an open or closed system at room temperature (5°C or higher but lower than 40°C, particularly 23°C ± 15°C). However, mixing in a closed system is preferred because hydrolysis and condensation reactions of the components will proceed if the mixing time is too long. The mixing time of components (A-1), (A-2), (A-3), and, if necessary, other components is preferably, for example, 1 second to 60 minutes, particularly 2 seconds to 30 minutes. The 1 or 2 second period applies when mixing is performed in a closed system by passing the mixture through a static mixer with an appropriate number of elements; longer times are preferred when mixing is performed using a dynamic mixer (the same applies hereinafter).

[0052] Next, the mixture of components (A-1), (A-2), (A-3), and, if necessary, other components is left to react at room temperature (5°C or higher but lower than 40°C, particularly 23°C ± 15°C) in a moisture-free environment for at least 6 hours, preferably 6 hours to 90 days, and more preferably 6 hours to 14 days. If the reaction is left to react for less than 6 hours, the reaction will not proceed sufficiently, and in step [II] described below, the mixture will thicken after the addition of component (B), impairing workability, or the thickening will progress to gel, making it impossible to produce a room-temperature-curable organopolysiloxane composition. To reach a temperature of 40°C or higher requires heating with a heat source, which is not only economically unprofitable but also causes problems such as the evaporation of components (A-2) and (A-3) and solidification on the inner wall surfaces of the headspace of the mixing device. Therefore, the reaction is carried out at room temperature below 40°C.

[0053] Furthermore, as described above, the static reaction is carried out in a moisture-blocking environment, and is preferably carried out in a sealed environment or in a state ventilated with or filled with dry air or an inert gas, for example, in a drum, container, or tank.

[0054] A mixture of components (A-1), (A-2), and (A-3) is mixed uniformly at room temperature (5°C or higher but lower than 40°C), and then allowed to react for 6 hours or longer at room temperature (5°C or higher but lower than 40°C). The resulting reaction mixture (A) contains an organopolysiloxane in which all hydroxyl groups in component (A-1) have been converted to reactive siloxy groups (e.g., alkoxysiloxy groups) as a result of the reaction of silanol groups (hydroxyl groups bonded to silicon atoms) in component (A-1) with reactive groups such as alkoxy groups in component (A-2) and / or (A-3), and unreacted main components such as components (A-2) and (A-3). In addition, the reaction mixture (A) contains terminal reactive groups (e.g., alkoxy groups) of the organopolysiloxane in which all hydroxyl groups in component (A-1) have been converted to reactive siloxy groups (e.g., alkoxysiloxy groups) and terminal reactive groups of component (A-2). These by-products include organopolysiloxanes of a wide variety of structures, such as organopolysiloxanes in which reactive groups such as alkoxy groups in component (A-3) have reacted with organopolysiloxanes in which all hydroxyl groups in component (A-1) have been converted to alkoxysiloxy groups (organopolysiloxanes in which all hydroxyl groups in component (A-1) have been converted to reactive siloxy groups), with some of the alkoxy groups having been hydrolyzed to hydroxyl groups; oligomer components formed when component (A-2) or (A-3) reacts with trace amounts of water present in the system; partially hydrolyzed components of component (A-2) or (A-3); and components that have undergone condensation reactions with each other and / or with each other to form partial hydrolyzed condensates. In addition, in the case of reaction product mixture (A) obtained by adding optional components (A-4), (A-5), and (A-6) to the mixture, many more by-products are contained.

[0055] In step [I] of the present invention, all of the terminal silanol groups in component (A-1) are reacted, and the resulting reaction product mixture (A) contains an organopolysiloxane in which the silanol groups (hydroxyl groups bonded to silicon atoms) in component (A-1) have reacted with reactive groups such as alkoxy groups in component (A-2) and / or (A-3), converting all of the hydroxyl groups in component (A-1) to reactive siloxy groups (e.g., alkoxysiloxy groups), and Only the silanol group (a hydroxyl group bonded to a silicon atom) at one end of component (1) reacts with a reactive group (e.g., an alkoxy group) in component (A-2) or (A-3), converting the hydroxyl group into a reactive siloxy group (e.g., an alkoxysiloxy group), and no organopolysiloxanes in which the silanol group at the other end remains intact, or organopolysiloxanes in which both unreacted molecular chain ends are blocked with silanol groups (i.e., component (A-1)), remain.

[0056] As mentioned above, the reaction product mixture (A) contains by-products consisting of an extremely large number of components, making it difficult to accurately identify the composition of the reaction product mixture (A) by analysis. However, it is possible to determine the remaining amounts of components (A-2) and (A-3), 29 The approximate proportion of components that have reacted with silanol groups in component (A-1) can be determined by analyzing the bonding state of silicon atoms in components (A-2) and (A-3) by Si-NMR, or by differences in the amount detected due to column adsorption in gel permeation chromatography analysis using a toluene mobile phase. According to the formulation and process of the present invention, the silanol groups in component (A-1) react with reactive groups (e.g., alkoxy groups) in components (A-2) and (A-3) to be converted to reactive siloxy groups (e.g., alkoxysiloxy groups), and the proportion of silanol groups in component (A-1) that have reacted with component (A-3) is estimated to be in the range of 0.001 to 70%.

[0057] After allowing the reaction to proceed for 6 hours or more at room temperature (5°C or higher but lower than 40°C), the reaction product mixture (A) can be used until it begins to thicken or gel significantly, as long as it is stored in a sealed container or stored under aeration of moisture-free dry air or an inert gas. However, in order to consistently obtain the properties of the room-temperature-curable organopolysiloxane composition of the present invention, it is preferable to use the reaction product mixture (A) within one year after allowing the reaction to proceed for 6 hours or more, more preferably within 90 days, and even more preferably within 14 days.

[0058] Next, step [II] will be described. Step [II] comprises a step of blending and uniformly mixing the reaction product mixture (A) obtained in step [I] above, (B) a curing catalyst, (C) an inorganic filler, and, if necessary, (A-2) a hydrolyzable organosilane compound represented by general formula (2) and / or a partial hydrolyzed condensate thereof, or (A-3) a silane coupling agent represented by general formula (3) and / or a partial hydrolyzed condensate thereof.

[0059] The hydrolyzable organosilane compound (A-2) represented by general formula (2) and / or its partial hydrolysis condensate may be blended in its entirety (100 mass%) in step [I] as described above, but since it also acts as a crosslinking agent (curing agent) for the composition, it can also be blended in step [II] and used as a crosslinking agent (curing agent) for the composition. The components (A-2) used in step [I] and step [II] may be the same or different.

[0060] When the (A-2) component is also blended in step [II], it is preferred that 0.2 to 10 parts by mass of the (A-2) component per 100 parts by mass of the (A-1) component be blended in step [I] in a proportion of 0.2 to 10 parts by mass (for example, 90 to 10% by mass, particularly 75 to 25% by mass), and the remainder of the (A-2) component be blended in step [II] in a proportion of 10 to 90% by mass, particularly 25 to 75% by mass.

[0061] Specifically, when the (A-2) component is blended in step [II], it is preferably blended in an amount of 0.02 to 8 parts by mass per 100 parts by mass of the (A-1) component (however, the total amount of steps [I] and [II] is 0.2 to 10 parts by mass per 100 parts by mass of the (A-1) component), particularly 0.05 to 7 parts by mass (however, the total amount of steps [I] and [II] is 0.2 to 9 parts by mass per 100 parts by mass of the (A-1) component), or even more preferably 0.06 to 6 parts by mass (however, the total amount of steps [I] and [II] is 0.2 to 8 parts by mass per 100 parts by mass of the (A-1) component). If the blending amount of the (A-2) component in step [II] is too high, the deep section curing of the resulting composition may be delayed, the elongation after curing may be reduced, or the adhesive performance may be reduced.

[0062] As described above, the silane coupling agent (A-3) represented by general formula (3) and / or its partial hydrolysis condensate may be blended in its entirety (100% by mass) in step [I]. However, since it not only acts as a catalyst and blocking agent for the blocking reaction of the terminal silanol groups of component (A-1) in step [I] but also as a component that imparts adhesion to the cured product (silicone rubber cured product) obtained from the composition of the present invention, it can also be blended in step [II] and used as an adhesion-imparting component. The components (A-3) used in step [I] and step [II] may be the same or different.

[0063] When the (A-3) component is also blended in step [II], it is preferred that 0.1 to 5 parts by mass of the (A-3) component per 100 parts by mass of the (A-1) component be blended in step [I] in a proportion of 0.1 to 5 parts by mass (for example, 90 to 10% by mass, particularly 75 to 25% by mass), and the remainder of the (A-3) component be blended in step [II] in a proportion of 10 to 90% by mass, particularly 25 to 75% by mass.

[0064] Specifically, when the (A-3) component is blended in step [II], it is preferably blended in an amount of 0.01 to 4 parts by mass per 100 parts by mass of the (A-1) component (however, the total amount of steps [I] and [II] is 0.1 to 5 parts by mass per 100 parts by mass of the (A-1) component), particularly 0.02 to 4 parts by mass (however, the total amount of steps [I] and [II] is 0.1 to 5 parts by mass per 100 parts by mass of the (A-1) component), and even more preferably 0.05 to 3 parts by mass (however, the total amount of steps [I] and [II] is 0.2 to 4 parts by mass per 100 parts by mass of the (A-1) component). If the blending amount of the (A-3) component in step [II] is too high, the deep section curing of the resulting composition may be delayed, the elongation after curing may be reduced, or the adhesive performance may be reduced.

[0065] [(B) Component] Examples of the curing catalyst of component (B) include organic carboxylates, alkoxides, and chelate compounds of metals such as tin, titanium, zirconium, aluminum, iron, antimony, bismuth, and manganese. More specific examples include organic tin compounds such as dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin dilaurate, dibutyltin maleate ester, dimethyltin dineodecanoate, dibutyltin dimethoxide, dioctyltin dineodecanoate [also known as dioctyltin diversatate], and stannous octoate; organic aluminum compounds such as aluminum tris(acetylacetonate), aluminum tris(ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate, and triethoxyaluminum; zirconium tetrakis( Examples of suitable alkoxy titanium compounds include titanium chelate compounds such as titanium dioxide, titanium dioxide chelate compounds, and amine compounds such as titanium dioxide, titanium dioxide chelate compounds, and amine compounds such as titanium dioxide, titanium dioxide chelate compounds, and amine compounds. These compounds may be used singly or in combination of two or more. In view of the good curability and excellent adhesiveness of the room-temperature-curable organopolysiloxane composition of the present invention, preferred are organic titanium compounds such as alkoxytitanium compounds and titanium chelate compounds, organic zirconium compounds, organic aluminum compounds, and organic tin compounds, and among these, alkoxytitanium compounds and titanium chelate compounds are more preferred. The curing catalyst of component (B) may be used alone or in combination of two or more different types.

[0066] The amount of component (B) added is 0.001 to 20 parts by mass, and preferably 0.1 to 15 parts by mass, per 100 parts by mass of component (A-1). If the amount of component (B) added is too small, the curing rate may be slow or curing may be insufficient, while if the amount is too large, the curing rate may be too fast, resulting in a loss of workability, a decrease in adhesive performance, a loss of stability during long-term storage, and economical disadvantages.

[0067] [(C) component] Component (C) is an inorganic filler, and examples thereof include calcium carbonate such as colloidal calcium carbonate and heavy calcium carbonate, fumed silica, aluminum oxide, aluminum hydroxide, talc, glass balloons, crystalline silica fine powder, amorphous silica fine powder, silica hydrogel, silica aerogel, diatomaceous earth, calcium silicate, aluminum silicate, titanium oxide, zinc oxide, ferrite, iron oxide, carbon black, graphite, mica, clay, bentonite, etc. Among these, those containing calcium carbonate and / or fumed silica are more preferred.

[0068] The calcium carbonate can be freely selected from calcium carbonate that has been surface-treated with a treating agent such as a fatty acid, a resin acid (rosin acid, etc.), or an alkali metal salt, alkaline earth metal salt, fatty acid ester, or quaternary ammonium salt thereof, or surface-untreated calcium carbonate. Examples of resin acids used here include abietic acid, dehydroabietic acid, dextropimaric acid, levopimaric acid, palustric acid, and sandaracopimaric acid. The fatty acid is not particularly limited, but is preferably one having 12 or more carbon atoms, such as stearic acid, oleic acid, palmitic acid, and lauric acid. The amount of the treating agent used is 3.0% by mass or less, particularly 0.5 to 2.5% by mass, based on the calcium carbonate. If the amount exceeds 3.0% by mass, the storage stability and adhesiveness of the composition will be impaired.

[0069] The calcium carbonate to be treated with the treating agent may be colloidal calcium carbonate having an average primary particle size of 0.1 μm or less, particularly 0.03 to 0.1 μm, or heavy calcium carbonate having an average primary particle size of more than 0.1 μm, which may be used alone or in combination. The particle size of colloidal calcium carbonate is a value measured by an electron microscope, and the particle size of heavy calcium carbonate is a value calculated from the specific surface area measured by an air permeability method.

[0070] Fumed silica is manufactured using a dry process from chlorosilane compounds, and has a BET specific surface area of ​​50m 2 / g or more, and more preferably 80 to 400m 2 The fumed silica is preferably surface-treated with an organosilicon compound such as a chlorosilane compound such as methyltrichlorosilane or dimethylchlorosilane, a silazane compound such as hexamethylsilazane, or a siloxane compound such as octamethylcyclotetrasiloxane, but if economical efficiency is prioritized, untreated fumed silica may be used as is.

[0071] In the present invention, when the (B) curing catalyst is a tin compound, the (C) inorganic filler is preferably fumed silica, and when the (B) curing catalyst is a titanium compound, the (C) inorganic filler is preferably calcium carbonate. In either case, fumed silica and calcium carbonate can be used in combination.

[0072] The inorganic filler of component (C) may be used alone or in combination of two or more different types. The blending amount of component (C) is 5 to 300 parts by mass, and preferably 10 to 200 parts by mass, per 100 parts by mass of component (A-1). If the blending amount of component (C) is too small, the thixotropy of the resulting composition decreases, and the necessary non-flowability is not achieved, resulting in reduced workability. If the blending amount of component (C) is too large, the viscosity becomes too high, making it impossible to work with.

[0073] [(D) component] In addition to the above-described components (A) to (C), the room-temperature-curable organopolysiloxane composition of the present invention may further contain, as an optional component (D), In one molecule, the following general formula (6) -OC(=O)CHR 8 (6) (In the formula, R 8 is a hydrogen atom or a monovalent hydrocarbon group. and β hydroxy groups (where α is an integer of 1 to 3, and β is 0, 1, or 2, and α+β=3 is satisfied). When the curing catalyst (B) is a titanium compound, it is more preferable to add the component (D).

[0074] The organic compound of component (D) having α fatty acid ester residues represented by general formula (6) above and β hydroxy groups per molecule has the effect of improving the storage stability of the room-temperature-curable organopolysiloxane composition of the present invention, and also serves to impart good mechanical properties to the cured product of the composition stored for long periods in a sealed container.

[0075] In the above general formula (6), R 8 R is a hydrogen atom or a monovalent hydrocarbon group, preferably a monovalent hydrocarbon group having 1 to 18 carbon atoms, and the monovalent hydrocarbon group may be a saturated monovalent hydrocarbon group (an alkyl group) or an unsaturated monovalent hydrocarbon group (for example, an alkenyl group), and may have a linear or branched structure. 8 Specific examples of include a hydrogen atom, alkyl groups such as a methyl group, an ethyl group, a heptadecyl group, an octadecyl group, and a 2-ethylhexyl group, and monovalent hydrocarbon groups such as a vinyl group and an alkenyl group such as an allyl group. In order to obtain a sufficient effect with a small amount added, a group with as small a molecular weight as possible is preferred, and among these, a hydrogen atom is more preferred.

[0076] In component (D), α, the number of fatty acid ester residues, is from 1 to 3, preferably 3. β, the number of hydroxy groups, is 0, 1 or 2, preferably 0. α+β, the sum of the fatty acid ester residues and hydroxy groups, is 3.

[0077] The component (D) is a compound represented by the general formula (6) above, where R 8 and the -OC(=O)- group. In other words, the fatty acid ester residue represented by the general formula (6) must be an ester residue of a carboxylic acid having two or more carbon atoms (an ester residue of a carboxylic acid having more carbon atoms than acetic acid), and the α-carbon adjacent to the carbonyl group C(=O) must be a primary carbon atom. When an ester compound in which the hydrogen atom of the -CH2- group in the general formula (6) is substituted with another organic group (e.g., an ester compound in which the α-carbon adjacent to the carbonyl group C(=O) is a branched secondary or tertiary carbon atom, such as glycerol tris(2-ethylhexanoate) or glycerol tris(neodecanoate)) is used as component (D), sufficient storage stability cannot be imparted to the composition of the present invention.

[0078] Furthermore, if a compound where α + β < 3 is used instead of the organic compound having α fatty acid ester residues and β hydroxy groups represented by general formula (6) in component (D), such as stearyl stearate, lauryl stearate, stearyl palmitate, lauryl palmitate, behenyl behenate, ethylene glycol distearate, ethylene glycol diacetate, propylene glycol diacetate, or linalyl acetate, the composition of the present invention will not have sufficient storage stability. Furthermore, if a compound where α + β ≥ 3 and α = 0 is used instead of the organic compound having α fatty acid ester residues and β hydroxy groups represented by general formula (6) in component (D), such as glycerin, trimethylolpropane, pentaerythritol, glucose, fructose, or cellulose, not only will it not provide sufficient adhesiveness to the composition of the present invention, but it will also have adverse effects such as a significant increase in the viscosity of the composition, making it unusable.

[0079] Component (D) is not particularly limited as long as it is an organic compound (hydrocarbon compound) having 1 to 3 fatty acid ester residues represented by general formula (6) and 0, 1, or 2 hydroxy groups, with a total of 3 fatty acid ester residues and hydroxy groups. As component (D), a fatty acid ester of a polyhydric alcohol having three hydroxy groups in one molecule and having a fatty acid ester residue represented by the above general formula (6) is preferably used, and more preferably a fatty acid ester of glycerin having a fatty acid ester residue represented by the above general formula (6) is used.

[0080] Specific examples of component (D) include triacetin, diacetin, monoacetin, tributyrin, tricaprylin, tristearin, glycerol diacetate laurate, trimethylolpropane tristearate, and trimethylolpropane triacetate. However, triacetin, diacetin, and monoacetin are preferred because they can produce a significant effect with a small amount added, and triacetin is particularly more preferred.

[0081] The component (D) may be used alone or in combination of two or more types. The amount of component (D) blended is 0.1 to 5 parts by mass, and preferably 0.5 to 2.5 parts by mass, per 100 parts by mass of component (A-1). If the amount of component (D) blended is less than the lower limit of the above range, the desired effects may not be obtained, while if it exceeds the upper limit of the above range, the adhesiveness of the composition will decrease.

[0082] In the production method of the present invention, component (D) is blended in step [II], but it can also be blended in step [I]. When component (D) is blended in step [I] as well, the blending ratio between step [I] and step [II] is preferably 1:9 to 9:1.

[0083] [(E) component] In addition to the above-described components (A) to (C), the room-temperature-curable organopolysiloxane composition of the present invention preferably contains, as an optional component, a silylating agent (E) as needed. Component (E) silylates trace amounts of alcohol compounds and the like that may be present in the composition, thereby further improving the storage stability of the composition and imparting good mechanical properties to a cured product of the room-temperature-curable organopolysiloxane composition of the present invention stored in a sealed container for extended periods. When the curing catalyst (B) is a tin compound, the inclusion of component (E) is more preferred.

[0084] Examples of the silylating agent for component (E) 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 hydroxy 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.

[0085] The component (E) may be used alone or in combination of two or more types. When component (E) is added, its amount is within the range of 0.1 to 10 parts by mass, and preferably within the range of 0.5 to 5 parts by mass, per 100 parts by mass of component (A-1). If the amount of component (E) is less than the lower limit of the above range, the desired effect may not be obtained, while if it is more than the upper limit of the above range, the odor may become strong and the composition may become expensive, which is not practical. The component (E) can be added in either step [I] and / or step [II] in the production method of the present invention.

[0086] [Other ingredients] Other components (additives) besides the above-mentioned components include monosilanols such as trimethylsilanol and diphenylmethylsilanol, dialkoxysilanes such as diphenyldimethoxysilane and dimethyldimethoxysilane, which are components for lowering the modulus of the cured silicone rubber product after curing, plasticizers, diluents such as dimethylpolysiloxanes capped with trimethylsiloxy groups at both ends, isoparaffins, platinum compounds as flame retardants, zinc carbonate powder, polyethers as thixotropy improvers if necessary, colorants such as pigments, dyes, and fluorescent brighteners, heat resistance improvers such as red iron oxide and cerium oxide, cold resistance improvers, rust inhibitors, mildew inhibitors, antibacterial agents, etc. These components can be added within a range that does not impair the objectives of the present invention. Solvents such as toluene, xylene, solvent volatile oil, cyclohexane, methylcyclohexane, and low-boiling point isoparaffins can also be added. The above-mentioned other components can be blended in either step [I] and / or step [II] in the production method of the present invention, but are preferably blended in step [II].

[0087] The room-temperature-curable organopolysiloxane composition of the present invention preferably does not contain a silane coupling agent containing an aromatic ring, in order to prevent the resulting cured silicone rubber from yellowing after exposure to ultraviolet light.

[0088] In the method for producing a room-temperature-curable organopolysiloxane composition of the present invention, step [II] involves blending and uniformly mixing the above-mentioned components (A) to (D), and, if necessary, components (A-2), (A-3), and / or other components, in a dry atmosphere and / or under reduced pressure and degassing, according to a conventional method, to produce a so-called one-component composition. The mixing temperature in step [II] may be room temperature (5°C or higher but lower than 40°C, particularly 23°C ± 15°C), and the mixing time is not particularly limited as long as it is long enough to uniformly mix the composition; the shorter the better, but a time of 1 second to 60 minutes, particularly 3 seconds to 30 minutes, is preferred.

[0089] In the best embodiment of the method for producing the room-temperature-curable organopolysiloxane composition of the present invention, the preparation of component (A) (step [I]) is carried out in-line using a raw material tank, piping, a mixer, a reactant tank, etc., and the addition and mixing (step [II]) of components (A) to (C), and optionally components (A-2), (A-3), and / or other components, is carried out in an in-line plant connected to the reactant tank by piping, using equipment capable of semi-continuous or continuous production without exposure to outside air.

[0090] The room-temperature-curable organopolysiloxane composition obtained by steps [I] and [II] above is preferably stored in a sealed package. Suitable packaging containers into which the composition can be directly filled include plastic cartridges, plastic cartridges wrapped around the outside with aluminum-laminated plastic film or a seal, aluminum-coated paper tube cartridges, pails, polyethylene bags used as inner bags for drums, aluminum-laminated plastic bags, sausage packs made of aluminum-laminated plastic film, metal tubes, plastic tubes, and other containers commonly used by those skilled in the art. Of these, containers with low moisture and oxygen permeability are preferred.

[0091] The room-temperature-curable organopolysiloxane composition obtained by the production method of the present invention will generally cure in the presence of moisture in the air when left in the atmosphere. The room-temperature-curable organopolysiloxane compositions obtained by the production method of the present invention can be used in a variety of applications, but are particularly effective as sealants and adhesives. [Example]

[0092] Examples and comparative examples of the present invention will be described below, but the present invention is not limited to these examples. The viscosity in the examples is a value measured using a rotational viscometer at 23°C. All compositions according to the present invention were prepared using a "mixing stirrer (model: 5DMV-01-r)" manufactured by Dalton Co., Ltd. (stirring tool: single type, rotation speed: 142 to 288 rpm). Room temperature refers to 23°C.

[0093] [Example 1] A mixture was prepared by uniformly mixing 100 parts by mass of dimethylpolysiloxane (viscosity 50,000 mPa s) in which both molecular chain terminals are blocked with hydroxyl groups (silanol groups) bonded to silicon atoms, 1.7 parts by mass of vinyltrimethoxysilane, 3.3 parts by mass of methyltrimethoxysilane, and 0.5 parts by mass of 3-aminopropyltrimethoxysilane at a room temperature of 23°C and atmospheric pressure for 10 minutes. After this, mixing was stopped and the mixture was allowed to stand for 24 hours in a sealed container at 23°C to allow the mixture to react, yielding reaction product mixture 1. All of the resulting reaction product mixture 1 was uniformly mixed with 100 parts by mass of fatty acid-treated colloidal calcium carbonate "Hakuenka CC-R (manufactured by Shiraishi Kogyo Co., Ltd.)" and 10 parts by mass of heavy calcium carbonate "OMYACARB-5-CN" (manufactured by OMYA Korea Co., Ltd.), and then 10 parts by mass of dimethylpolysiloxane (viscosity 100 mPa s) in which both molecular chain terminals are blocked with trimethylsiloxy groups, 1 part by mass of triacetin, and 3 parts by mass of diisopropoxybis(ethylacetoacetate)titanium were added. The mixture was mixed at 23°C under reduced pressure for 30 minutes while removing air bubbles until uniform, thereby preparing composition 1.

[0094] [Example 2] Composition 2 was prepared in the same manner as in Example 1, except that in Example 1, the amount of 3-aminopropyltrimethoxysilane was changed from 0.5 parts by mass to 0.3 parts by mass, and 0.2 parts by mass of 3-(2-aminoethylamino)propyltrimethoxysilane was further used to obtain reaction product mixture 2, and reaction product mixture 2 was used instead of reaction product mixture 1.

[0095] [Example 3] A mixture was prepared by uniformly mixing 100 parts by mass of dimethylpolysiloxane (viscosity 50,000 mPa·s) in which both molecular chain terminals are capped with hydroxyl groups (silanol groups) bonded to silicon atoms, 1.7 parts by mass of vinyltrimethoxysilane, 3.3 parts by mass of methyltrimethoxysilane, and 1.3 parts by mass of 3-aminopropyltrimethoxysilane at room temperature of 23°C and atmospheric pressure for 10 minutes. After stopping the mixing, the mixture was allowed to stand for 24 hours in a sealed container at 23°C to react, yielding reaction product mixture 3. The entirety of the obtained reaction product mixture 3, 42 parts by mass of dimethylpolysiloxane (viscosity 100 mPa·s) in which both molecular chain terminals are capped with trimethylsiloxy groups, 0.3 parts by mass of 3-aminopropyltrimethoxysilane, and a 105 m2 olefin copolymer having a BET specific surface area were mixed together. 2 Composition 3 was prepared by uniformly mixing 15 parts by mass of fumed silica ("MU-215" manufactured by Shin-Etsu Chemical Co., Ltd.) having a surface treated with dimethyldichlorosilane (1 / g), followed by adding 0.8 parts by mass of hexamethyldisilazane and 0.2 parts by mass of dioctyltin diversatate under reduced pressure while removing air bubbles over 10 minutes until the mixture was uniform.

[0096] [Example 4] A mixture was prepared by uniformly mixing 100 parts by mass of dimethylpolysiloxane (viscosity 14,000 mPa s) in which both molecular chain terminals are capped with silicon-bonded hydroxyl groups (silanol groups), 49 parts by mass of dimethylpolysiloxane (viscosity 14,000 mPa s) in which one molecular chain terminal is capped with a silicon-bonded hydroxyl group (silanol group) and the other molecular chain terminal is capped with a trimethylsilyl group, 5.5 parts by mass of dimethylpolysiloxane (viscosity 14,000 mPa s) in which both molecular chain terminals are capped with trimethylsiloxy groups, 1.8 parts by mass of vinyltrimethoxysilane, 5.5 parts by mass of methyltrimethoxysilane, and 1.5 parts by mass of 3-aminopropyltrimethoxysilane at room temperature of 23°C and atmospheric pressure for 10 minutes. After stopping the mixing, the mixture was allowed to stand for 24 hours in a sealed container at 23°C to allow the reaction to proceed, yielding reaction product mixture 4. The entire reaction product mixture 4 obtained, 0.3 parts by mass of 3-(2-aminoethyl)aminopropyltrimethoxysilane, and a 105 m 2 Composition 4 was prepared by uniformly mixing 16.4 parts by mass of fumed silica ("MU-215" manufactured by Shin-Etsu Chemical Co., Ltd.) having a surface treated with dimethyldichlorosilane (16.4 parts by mass of fumed silica) at 1 / g, and then adding 0.9 parts by mass of hexamethyldisilazane and 0.2 parts by mass of dioctyltin diversatate. The mixture was mixed under reduced pressure for 10 minutes while removing air bubbles until uniform, thereby preparing composition 4.

[0097] [Example 5] A mixture was prepared by uniformly mixing 100 parts by mass of dimethylpolysiloxane (viscosity 14,000 mPa s) in which both molecular chain terminals are capped with silicon-bonded hydroxyl groups (silanol groups), 49 parts by mass of dimethylpolysiloxane (viscosity 14,000 mPa s) in which one molecular chain terminal is capped with a silicon-bonded hydroxyl group (silanol group) and the other molecular chain terminal is capped with a trimethylsilyl group, 5.5 parts by mass of dimethylpolysiloxane (viscosity 14,000 mPa s) in which both molecular chain terminals are capped with trimethylsiloxy groups, 0.9 parts by mass of vinyltrimethoxysilane, 3.6 parts by mass of methyltrimethoxysilane, and 0.9 parts by mass of 3-aminopropyltrimethoxysilane at room temperature of 23°C and atmospheric pressure for 10 minutes. After stopping the mixing, the mixture was allowed to stand for 24 hours in a sealed container at 23°C to react, yielding reaction product mixture 5. The entire reaction product mixture 5 obtained, 0.8 parts by mass of 3-aminopropyltrimethoxysilane, and a 105 m 2 Composition 5 was prepared by uniformly mixing 16.4 parts by mass of fumed silica ("MU-215" manufactured by Shin-Etsu Chemical Co., Ltd.) having a surface treated with dimethyldichlorosilane (16.4 parts by mass of fumed silica) at 1 / g, and then adding 0.9 parts by mass of hexamethyldisilazane and 0.2 parts by mass of dioctyltin diversatate. The mixture was mixed under reduced pressure for 10 minutes while removing air bubbles until uniform, thereby preparing composition 5.

[0098] [Comparative Example 1] Composition 6 was prepared in the same manner as in Example 1, except that in Example 1, 1.7 parts by mass of vinyltrimethoxysilane was not added, the amount of methyltrimethoxysilane added was changed from 3.3 parts by mass to 5 parts by mass, and further, 0.5 parts by mass of 3-aminopropyltrimethoxysilane was not added but instead 1.7 parts by mass of 3-(2-aminoethylamino)propyltrimethoxysilane was used to obtain reaction product mixture 6, and reaction product mixture 6 was used instead of reaction product mixture 1.

[0099] Comparative Example 2 Composition 7 was prepared in the same manner as in Comparative Example 1, except that reaction product mixture 7 was obtained by using 0.5 parts by mass of 3-aminopropyltrimethoxysilane instead of 1.7 parts by mass of 3-(2-aminoethylamino)propyltrimethoxysilane in Comparative Example 1, and reaction product mixture 7 was used instead of reaction product mixture 6.

[0100] Comparative Example 3 Composition 8 was prepared in the same manner as in Comparative Example 2, except that the amount of 3-aminopropyltrimethoxysilane in Comparative Example 2 was changed from 0.5 parts by mass to 1.7 parts by mass to obtain reaction product mixture 8, and reaction product mixture 8 was used instead of reaction product mixture 7.

[0101] Comparative Example 4 Composition 9 was prepared in the same manner as in Comparative Example 1, except that the amount of 3-(2-aminoethylamino)propyltrimethoxysilane in Comparative Example 1 was changed from 1.7 parts by mass to 0.3 parts by mass to obtain reaction product mixture 9, and reaction product mixture 9 was used instead of reaction product mixture 6.

[0102] Comparative Example 5 In Example 3, 1.7 parts by mass of vinyltrimethoxysilane was not added, the amount of methyltrimethoxysilane added was changed from 3.3 parts by mass to 5 parts by mass, and further, 1.3 parts by mass of 3-aminopropyltrimethoxysilane was not added but instead 0.3 parts by mass of 3-(2-aminoethylamino)propyltrimethoxysilane was used to obtain reaction product mixture 10, and reaction product mixture 10 was used instead of reaction product mixture 3, and composition 10 was prepared in the same manner as in Example 3 except that 0.3 parts by mass of 3-aminopropyltrimethoxysilane was not added.

[0103] Comparative Example 6 In Example 3, 1.7 parts by mass of vinyltrimethoxysilane was not added, the amount of methyltrimethoxysilane added was changed from 3.3 parts by mass to 5 parts by mass, and further, 1.3 parts by mass of 3-aminopropyltrimethoxysilane was not added but instead 1.7 parts by mass of 3-(2-aminoethylamino)propyltrimethoxysilane was used to obtain reaction product mixture 11, and reaction product mixture 11 was used instead of reaction product mixture 3, and composition 11 was prepared in the same manner as in Example 3 except that 0.3 parts by mass of 3-aminopropyltrimethoxysilane was not added.

[0104] Comparative Example 7 Composition 12 was prepared in the same manner as in Example 1, except that in Example 1, 0.5 parts by mass of 3-aminopropyltrimethoxysilane was not added, but instead 0.3 parts by mass of 3-(2-aminoethylamino)propylmethyldimethoxysilane was used to obtain reaction product mixture 12, and reaction product mixture 12 was used instead of reaction product mixture 1.

[0105] The room-temperature-curable organopolysiloxane compositions of Examples 1 to 5 and Comparative Examples 1 to 7 were checked for thickening or gelation during preparation to evaluate the difficulty of production. The resulting room-temperature-curable organopolysiloxane compositions were also evaluated for the following performance characteristics (curability after storage, low-temperature adhesion development, discoloration after high-temperature heating, and dents on the joint surface after construction of calcium silicate board joints). These results are shown in Tables 1 to 3.

[0106] [Manufacturing difficulties] In step [II], it was confirmed whether thickening or gelation occurred. The presence or absence of the Weissenberg phenomenon was visually observed to determine whether thickening occurred. The presence or absence of the Weissenberg phenomenon was considered to be an increase in viscosity, and gelation was determined by visually observing the composition. The absence of thickening or gelation was recorded as "none."

[0107] [Cureability after storage] Each composition obtained in the above Examples and Comparative Examples was filled into a 330 ml polyethylene cartridge for sealants made of polyethylene, and sealed with a polyethylene inner stopper. The sealed cartridge was placed in a thermostatic chamber at 70°C and stored for 7 days. After removal, the cartridge was left to stand for 24 hours at 23°C and 50% relative humidity. The tack-free time was measured using the composition in the cartridge. If no adhesion of the composition to the polyethylene sheet occurred after 120 minutes, the test was judged as passing, and if adhesion was observed, the test was judged as failing. The tack-free time was measured according to the method specified in ASTM C679 at 23°C and 50% relative humidity.

[0108] [Low temperature adhesion] Each composition obtained in the above Examples and Comparative Examples was extruded onto an aluminum panel (fluororesin-coated aluminum) coated with "YJ2443 (manufactured by KCC)," a high-temperature bakeable fluororesin paint, and formed into a thin sheet 0.3 mm thick. The sheet was then placed in a chamber adjusted to a temperature of 10°C and a relative humidity of 30-50%, and curing began. After 24 hours, the cured sheet was scratched with a fingernail. If the sheet peeled at the interface from the aluminum panel, it was judged as "fail," and if there was no interfacial peeling and cohesive failure occurred, it was judged as "pass."

[0109] [Discoloration after high temperature heating] Each composition obtained in the above Examples and Comparative Examples was extruded into a polyethylene frame on a polyethylene sheet, molded into a 2 mm thick sheet, and cured by leaving it to stand for 7 days in an environment of 23°C and 50% relative humidity. The resulting cured product was placed in a chamber at 90°C and left to stand for 7 days, then removed and visually observed for any change in color from before placing it in the chamber. If significant yellowing was observed, it was judged as failing (yes), and if no significant yellowing was observed, it was judged as passing (no).

[0110] [Dent on the joint surface after calcium silicate board joint construction] A 10 mm wide joint was made on the cut surface of a 6 mm thick calcium silicate board, and the joint was filled with each composition obtained in the above Examples and Comparative Examples immediately after preparation. The composition was then left to cure for 7 days at 23°C and 50% relative humidity. After that, the composition was left for 3 months at 23°C and 50% relative humidity, and the width of the depression in the center of the joint was measured. A value of 1 mm or less was judged to be acceptable, and a value of more than 1 mm was judged to be unacceptable.

[0111] [Table 1]

[0112] [Table 2]

[0113] [Table 3]

Claims

1. [I]: (A-1) The following general formula (1) 【Chemistry 1】 (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and m is an integer of 10 or greater. 100 parts by mass of an organopolysiloxane represented by the formula (I) having both molecular chain terminals blocked with silanol groups and a viscosity at 23°C of 20 to 1,000,000 mPa s, (A-2) The following general formula (2) 【Chemistry 2】 (In the formula, R 2 is a vinyl group, and R 3 are independently unsubstituted monovalent hydrocarbon groups having 1 to 3 carbon atoms, and a is 3 or 4. and / or a partial hydrolysis condensate thereof: 0.2 to 10 parts by mass, (A-3) The following general formula (3) 【Transformation 3】 (In the formula, R 5 is an aliphatic divalent hydrocarbon group having 1 to 10 carbon atoms, and R 6 and R 7 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and b is 2 or 3. and / or a partial hydrolysis condensate thereof: 0.1 to 5 parts by mass uniformly mixed at room temperature (5°C or higher but lower than 40°C), and then allowed to react at room temperature in a moisture-blocking environment for 6 hours or more to obtain a reaction product mixture (A); [II]: The reaction product mixture (A) is The component (A-2): 0 to 8 parts by mass (however, the total amount of the components in steps [I] and [II] is 0.2 to 10 parts by mass per 100 parts by mass of the component (A-1)), The component (A-3): 0 to 4 parts by mass (however, the total amount of the components in steps [I] and [II] is 0.1 to 5 parts by mass per 100 parts by mass of the component (A-1)), (B) Curing catalyst: 0.001 to 20 parts by mass, and (C) Inorganic filler: 5 to 300 parts by mass A process of blending and mixing the above ingredients evenly A method for producing a room-temperature-curable organopolysiloxane composition comprising:

2. In the above step [I] and / or step [II], (A-4) The following general formula (4) 【Chemistry 4】 (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and m is an integer of 10 or greater. and a viscosity at 23°C of 20 to 1,000,000 mPa·s, wherein one end is blocked with a silanol group and the other end is blocked with a triorganosilyl group: 0.1 to 100 parts by mass in total for step [I] and step [II] per 100 parts by mass of component (A-1).

2. A method for producing the room-temperature-curable organopolysiloxane composition of claim 1, comprising:

3. In the above step [I] and / or step [II], (A-5) The following general formula (5) 【Transformation 5】 (In the formula, R 4 is an aliphatic divalent hydrocarbon group having 2 to 10 carbon atoms, and R 5 is an aliphatic divalent hydrocarbon group having 1 to 10 carbon atoms, and R 6 and R 7 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and b is 2 or 3. and / or a partial hydrolysis condensate thereof: 0.1 to 5 parts by mass in total for step [I] and step [II] per 100 parts by mass of component (A-1) 2. A method for producing the room-temperature-curable organopolysiloxane composition of claim 1, comprising:

4. (A-1) The following general formula (1) 【Transformation 6】 (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and m is an integer of 10 or greater. 100 parts by mass of an organopolysiloxane represented by the formula (I) having both molecular chain terminals blocked with silanol groups and a viscosity at 23°C of 20 to 1,000,000 mPa s, (A-2) The following general formula (2) 【Transformation 7】 (In the formula, R 2 is a vinyl group, and R 3 are independently unsubstituted monovalent hydrocarbon groups having 1 to 3 carbon atoms, and a is 3 or 4. and / or a partial hydrolysis condensate thereof: 0.2 to 10 parts by mass, (A-3) The following general formula (3) 【Transformation 8】 (In the formula, R 5 is an aliphatic divalent hydrocarbon group having 1 to 10 carbon atoms, and R 6 and R 7 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and b is 2 or 3. and / or a partial hydrolysis condensate thereof: 0.1 to 5 parts by mass a reaction product mixture (A) obtained by allowing a mixture of the above-mentioned components to react at room temperature in a moisture-blocking environment for 6 hours or more; The component (A-2): 0 to 8 parts by mass (however, the amount of the component (A-1) in the entire composition is 0.2 to 10 parts by mass per 100 parts by mass of the component (A-1)), The component (A-3): 0 to 4 parts by mass (however, the amount of the component (A-1) in the entire composition is 0.1 to 5 parts by mass per 100 parts by mass of the component (A-1)), (B) Curing catalyst: 0.001 to 20 parts by mass, and (C) Inorganic filler: 5 to 300 parts by mass A room temperature curable organopolysiloxane composition comprising:

5. The reaction product mixture (A) further comprises: (A-4) The following general formula (4) 【Chemistry 9】 (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and m is an integer of 10 or greater. an organopolysiloxane represented by the formula (I) having one end blocked with a silanol group and the other end blocked with a triorganosilyl group and having a viscosity at 23°C of 20 to 1,000,000 mPa·s, per 100 parts by mass of component (A-1); 5. The room-temperature-curable organopolysiloxane composition according to claim 4, which is obtained by reacting a mixture containing

6. The component (A-5) is a compound represented by the following general formula (5): 【Chemistry 10】 (In the formula, R 4 is an aliphatic divalent hydrocarbon group having 2 to 10 carbon atoms, and R 5 is an aliphatic divalent hydrocarbon group having 1 to 10 carbon atoms, and R 6 and R 7 are each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and b is 2 or 3. and / or a partial hydrolysis condensate thereof in an amount of 0.1 to 5 parts by mass per 100 parts by mass of component (A-1) in the following embodiment (i) and / or (ii): (i) The reaction product mixture (A) is obtained by reacting a mixture containing the component (A-5). (ii) The composition contains the component (A-5) as the sole component.

7. Furthermore, (D) contains, in one molecule, a compound represented by the following general formula (6): -OC(=O)CH 2 R 8 (6) (In the formula, R 8 is a hydrogen atom or a monovalent hydrocarbon group. and β hydroxy groups (wherein α is an integer of 1 to 3, β is 0, 1, or 2, and α+β=3 is satisfied). 0.1 to 5 parts by mass per 100 parts by mass of component (A-1) 5. The room temperature curable organopolysiloxane composition according to claim 4, comprising:

8. 8. The room-temperature-curable organopolysiloxane composition according to claim 7, wherein component (D) is a fatty acid ester of a polyhydric alcohol having three hydroxy groups per molecule and having a fatty acid ester residue represented by general formula (6):

9. 8. The room-temperature-curable organopolysiloxane composition according to claim 7, wherein component (D) is a fatty acid ester of glycerin having a fatty acid ester residue represented by general formula (6).

10. 8. The room-temperature-curable organopolysiloxane composition according to claim 7, wherein component (D) is at least one member selected from the group consisting of triacetin, diacetin, and monoacetin.

11. Furthermore, (E) a silylating agent: 0.1 to 10 parts by mass per 100 parts by mass of the component (A-1) 5. The room-temperature-curable organopolysiloxane composition according to claim 4, comprising:

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