Organosilicon compound, method for producing same, and additive

Abstract

When the novel organosilicon compound represented by formula (1) is added to a condensation-curable room-temperature-curable resin composition, the tensile strength and adhesive strength of a cured product of the composition can be improved, and thus the novel organosilicon compound can be used as an additive for improving the strength of the cured product of the condensation-curable room-temperature-curable resin composition. (In the formula, R1 is an unsubstituted or substituted monovalent hydrocarbon group having 1-12 carbon atoms excluding an aliphatic unsaturated bond, R2 is a hydrogen atom or an aliphatic unsaturated monovalent hydrocarbon group having 2-12 carbon atoms, R3 is an unsubstituted or substituted monovalent hydrocarbon group having 1-12 carbon atoms excluding an aliphatic unsaturated bond, A is a divalent hydrocarbon group having 2-8 carbon atoms, k is an integer of 0-2, m is an integer of 3-6, and n is an integer of 0-2. K + m is an integer from 3 to 8, and n is an integer from 0 to 100. ).

Description

Technical Field

[0001] This invention relates to novel organosilicon compounds, and more particularly to organosilicon compounds suitable for use as additives that help improve the strength of cured products of condensation-curing room temperature curing resin compositions, methods for manufacturing the same, and additives for use in condensation-curing room temperature curing resin compositions. Background Technology

[0002] To date, condensation-curing type room-temperature curing resin compositions, such as condensation-curing type organopolysiloxane compositions, are known as cross-linking resin compositions that cross-link and cure to form an elastomer (cured rubber) through a condensation reaction with moisture (humidity) in the air at room temperature (23℃±15℃). These room-temperature curing organopolysiloxane compositions are widely used in construction, conveyor systems, and electrical and electronic components due to their safety, rubber-like durability, and excellent adhesion. In particular, the tensile strength and adhesive strength of the cured product are crucial to the reliability of the components used and are therefore highly valued.

[0003] In room temperature curing organopolysiloxane compositions, the so-called one-component (one-liquid) room temperature curing organopolysiloxane compositions do not require weighing the base polymer, crosslinking agent, catalyst, etc. before use, do not require complicated mixing, and do not produce mixing errors. Moreover, even without the use of a primer, they have excellent adhesion to a wide range of substrates. Therefore, they are widely used as elastic adhesives and coating materials in the electrical and electronic industries, as well as as sealing materials for buildings.

[0004] When such single-component, room-temperature curing organopolysiloxane compositions come into contact with moisture in the air, they are often classified according to the types of compounds released from the composition. Representative examples include acetic acid-free, oxime-free, amide-free, hydroxylamine-free, acetone-free, and alcohol-free organopolysiloxane compositions. Among them, oxime-free organopolysiloxane compositions that cure by releasing oximes have excellent storage stability and can produce excellent cured films in a short time. In addition, alcohol-free organopolysiloxane compositions that cure by releasing alcohols have low odor, do not corrode metals such as copper and iron, have excellent self-adhesion (adhesion to various substrates after curing without the use of a primer), and excellent adhesion durability. They have been used in fields that utilize these characteristics.

[0005] However, it is known that the cured products of generally single-component room temperature curing organopolysiloxane compositions have low tensile strength and adhesive strength.

[0006] In single-component room temperature curing organopolysiloxane compositions, the method of adding fillers such as silica and colloidal calcium carbonate to the filler as a way to improve the tensile strength and adhesive strength of the cured product (Non-Patent Document 1) has long been known.

[0007] However, regarding fillers, if the amount added is increased excessively, the viscosity of the composition will increase significantly, resulting in limitations such as reduced workability during use, and further methods are needed.

[0008] Existing technical documents

[0009] Patent documents

[0010] Non-Patent Literature 1: Kunio Ito, "Handbook of Organosilicon", Nikkan Kogyo Shimbun, 1990 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] Therefore, the present invention was made in view of the above-mentioned actual situation, and its object is to provide a novel organosilicon compound and a method for manufacturing the same, which can be used as an additive to improve the strength of the cured product of a condensation-curing room temperature curing resin composition by adding it to a condensation-curing room temperature curing organopolysiloxane composition (so-called organosilicon RTV rubber composition).

[0013] Methods for solving problems

[0014] In order to achieve the above objectives, the inventors conducted in-depth research and found that when the novel organosilicon compound represented by formula (1) is added to a condensation-curing room temperature curing resin composition such as a condensation-curing room temperature curing organopolysiloxane composition, the tensile strength and adhesive strength of the cured composition can be improved. Therefore, it can be used as an additive to improve the strength of the cured product of the condensation-curing room temperature curing resin composition, thus completing the present invention.

[0015] That is, the present invention provides the following organosilicon compounds, methods for manufacturing the same, and additives.

[0016] [1] Organosilicon compounds represented by the following formula (1).

[0017] [Chemistry 1]

[0018]

[0019] (where R is in the formula) 1 R is a monovalent hydrocarbon group consisting of 1 to 12 unsubstituted or substituted carbon atoms, excluding aliphatic unsaturated bonds. 2R is a hydrogen atom or an aliphatic unsaturated monovalent hydrocarbon group with 2 to 12 carbon atoms. 3 A represents a monovalent hydrocarbon group with 1 to 12 unsubstituted or substituted carbon atoms (excluding aliphatic unsaturated bonds), A represents a divalent hydrocarbon group with 2 to 8 carbon atoms, k represents an integer from 0 to 2, m represents an integer from 3 to 6, k+m represents an integer from 3 to 8, and n represents an integer from 0 to 100.

[0020] [2] The organosilicon compound according to [1] is an additive used to improve the strength of the cured product of a condensation-curing room temperature curing resin composition.

[0021] [3] The method for manufacturing organosilicon compounds according to [1] or [2] includes a step of carrying out a hydrosilane or organohydropolysiloxane represented by the following formula (2) and a cyclic organopolysiloxane represented by the following formula (3) in the presence of a catalyst containing a platinum compound to perform a hydrosilanization addition reaction.

[0022] [Chemistry 2]

[0023]

[0024] (where R is in the formula) 3 (This refers to a monovalent hydrocarbon group with 1 to 12 unsubstituted or substituted carbon atoms, excluding aliphatic unsaturated bonds, where n is an integer from 0 to 100.)

[0025] [Chemistry 3]

[0026]

[0027] (where R is in the formula) 1 R is a monovalent hydrocarbon group consisting of 1 to 12 unsubstituted or substituted carbon atoms, excluding aliphatic unsaturated bonds. 2’ (Aliphatic unsaturated monovalent hydrocarbon group with 2 to 12 carbon atoms, k is an integer from 0 to 2, m is an integer from 3 to 6, and k+m is an integer from 3 to 8.)

[0028] [4] The method for manufacturing organosilicon compounds according to [1] or [2] includes a step of subjecting an organosilicon or organopolysiloxane represented by formula (4) to a cyclic organohydrogen polysiloxane represented by formula (5) in the presence of a catalyst containing a platinum compound for a hydrosilylation addition reaction.

[0029] [Chemistry 4]

[0030]

[0031] (where R is in the formula) 2’ R is an aliphatic unsaturated monovalent hydrocarbon group with 2 to 12 carbon atoms. 3(This refers to a monovalent hydrocarbon group with 1 to 12 unsubstituted or substituted carbon atoms, excluding aliphatic unsaturated bonds, where n is an integer from 0 to 100.)

[0032] [Chemistry 5]

[0033]

[0034] (where R is in the formula) 1 (This refers to a monovalent hydrocarbon group with 1 to 12 unsubstituted or substituted carbon atoms, excluding aliphatic unsaturated bonds; k is an integer from 0 to 2; m is an integer from 3 to 6; and k+m is an integer from 3 to 8.)

[0035] [5] An additive for condensation-curing room temperature curing resin compositions comprising an organosilicon compound according to [1] or [2].

[0036] [6] According to the additive described in [5], wherein the condensation-curing room temperature curing resin composition is a condensation-curing room temperature curing organopolysiloxane composition.

[0037] The organosilicon compounds of the present invention as defined above are included in the present invention as long as the average structure of the organosilicon compound aggregate is within the above range, even if there are structural differences between the individual organosilicon compounds.

[0038] The effects of the invention

[0039] The organosilicon compound of the present invention is a novel organosilicon compound that can be used as an additive to improve the strength of condensation-curing room temperature curing resin compositions such as condensation-curing room temperature curing organopolysiloxane compositions (so-called organosilicon RTV rubber compositions). Detailed Implementation

[0040] The present invention will now be described in detail.

[0041] <Organosilicon compounds>

[0042] The organosilicon compound of the present invention is derived from the following formula (1).

[0043] [Chemistry 6]

[0044]

[0045] (where R is in the formula) 1 R is a monovalent hydrocarbon group consisting of 1 to 12 unsubstituted or substituted carbon atoms, excluding aliphatic unsaturated bonds. 2 R is a hydrogen atom or an aliphatic unsaturated monovalent hydrocarbon group with 2 to 12 carbon atoms. 3A represents a monovalent hydrocarbon group with 1 to 12 unsubstituted or substituted carbon atoms (excluding aliphatic unsaturated bonds), A represents a divalent hydrocarbon group with 2 to 8 carbon atoms, k represents an integer from 0 to 2, m represents an integer from 3 to 6, k+m represents an integer from 3 to 8, and n represents an integer from 0 to 100.

[0046] The indicated cyclic organopolysiloxane compound is a polyfunctional cyclic organopolysiloxane compound containing a silanol group, which has 3 to 6 (i.e., m) monovalent organosiloxane groups, consisting of a divalent hydrocarbon group (A) having a diorganohydroxysilyl group or a terminal silanol group (hydroxyl group bonded to a silicon atom), as monovalent substituents (side chains) bonded to the silicon atoms of the cyclic organopolysiloxane consisting of 3 to 8 (i.e., (k+m)) siloxane units.

[0047] In equation (1) above, R is used as... 1 The term refers to monovalent hydrocarbon groups with 1 to 12 unsubstituted or substituted carbon atoms, excluding aliphatic unsaturated bonds. Examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, tolyl, xylyl, and α-, β-naphthyl; and aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl. Additionally, groups formed by substituting some or all of the hydrogen atoms of these groups with halogen atoms such as F, Cl, Br, or cyano groups, such as 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl. Among these, R... 1 Preferably, lower alkyl groups such as methyl, ethyl, isopropyl, and butyl or aryl groups such as phenyl are preferred, with methyl and phenyl being particularly preferred.

[0048] In the above equation (1), R 2 Among the aliphatic unsaturated monovalent hydrocarbon groups representing 2 to 12 hydrogen atoms, examples of aliphatic unsaturated monovalent hydrocarbon groups with 2 to 12 carbon atoms include alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, and cyclohexenyl; and alkynyl groups such as ethynyl (ethynyl) and ethynylmethyl. Among these, R... 2 The preferred groups are hydrogen atoms or alkenyl groups such as vinyl and allyl, with hydrogen atoms and vinyl groups being particularly preferred.

[0049] In equation (1) above, as a result of R 3 The unsubstituted or substituted monovalent hydrocarbon groups with 1 to 12 carbon atoms, excluding aliphatic unsaturated bonds, can be listed as R as described above. 1The same group as the example group can include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, tolyl, xylyl, and α-,β-naphthyl; and aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl. Additionally, groups formed by substituting some or all of the hydrogen atoms of these groups with halogen atoms such as F, Cl, and Br, or cyano groups, such as 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl. Among these, R... 3 Preferably, lower alkyl groups such as methyl, ethyl, isopropyl, and butyl or aryl groups such as phenyl are preferred, with methyl and phenyl being particularly preferred.

[0050] In the above formula (1), A is a divalent hydrocarbon group such as an alkylene group or an alkenylene group with 2 to 8 carbon atoms, preferably with 2 to 4 carbon atoms, and preferably -(CH2). p -(p represents an integer from 2 to 8, preferably an integer from 2 to 4.) and other alkylene groups. Among these, -CH2CH2- and -CH2CH2CH2- are more preferred.

[0051] In the above formula (1), k is an integer from 0 to 2, preferably 0 or 1.

[0052] In the above formula (1), m is an integer from 3 to 6, preferably 4 or 5.

[0053] In the above formula (1), k+m is an integer from 3 to 8, preferably an integer from 4 to 6.

[0054] In the above formula (1), n ​​is an integer from 0 to 100, preferably an integer from 0 to 20, more preferably an integer from 0 to 10, and even more preferably an integer from 0 to 4.

[0055] <Methods for manufacturing organosilicon compounds>

[0056] The organosilicon compound represented by the above formula (1) of the present invention can be manufactured by a method including the following steps [I] or [II].

[0057] [I] Make the following equation (2) work.

[0058] [Chemistry 7]

[0059]

[0060] (where R is in the formula) 3 (The values ​​of 'n' and 'n' are the same as above.)

[0061] The organohydrosilane or organohydropolysiloxane represented by the following formula (3) is related to the organohydrosilane or organohydropolysiloxane.

[0062] [Chemistry 8]

[0063]

[0064] (where R is in the formula) 1 The values ​​of ,k,m,k+m are the same as above, and R 2’ It is an aliphatic unsaturated monovalent hydrocarbon group with 2 to 12 carbon atoms.

[0065] The process described involves the hydrosilylation addition reaction of a cyclic organopolysiloxane in the presence of a catalyst containing a platinum compound.

[0066] [II] From the following formula (4)

[0067] [Chemistry 9]

[0068]

[0069] (where R is in the formula) 3 The values ​​of n and R are the same as above. 2’ It is an aliphatic unsaturated monovalent hydrocarbon group with 2 to 12 carbon atoms.

[0070] The organosilane or organopolysiloxane represented is related to the following formula (5).

[0071] [Chemistry 10]

[0072]

[0073] (where R is in the formula) 1 (k, m, and k+m are the same as above.)

[0074] The process described involves the hydrosilylation addition reaction of a cyclic organohydrogen polysiloxane in the presence of a catalyst containing a platinum compound.

[0075] Specifically, this is achieved by using an organohydrosilane represented by formula (2) above, which has a silanol group (hydroxyl group bonded to a silicon atom) and a hydrogen atom bonded to a silicon atom (hydrosilyl group represented by SiH) in the molecule (in the case of n=0 in formula (2)) or an organohydropolysiloxane with a silanol group at one end of the molecular chain and a hydrogen atom bonded to a silicon atom at the other end of the molecular chain (in the case of n=1 to 100 in formula (2)), and an organohydropolysiloxane represented by formula (3) above, which has an alkenyl group, alkynyl group, etc., and an aliphatic unsaturated monovalent hydrocarbon group (R) 2’ Cyclic organopolysiloxanes are subjected to hydrosilylation addition reactions in the presence of a catalyst containing platinum compounds, or, the cyclic organopolysiloxanes represented by the above formula (4) having aliphatic unsaturated monovalent hydrocarbon groups (R, silanol, alkenyl, alkynyl, etc.) in the molecule are subjected to such reactions. 2’ Organosilanes (in the case of n=0 in formula (4)) or those with aliphatic unsaturated monovalent hydrocarbon groups such as alkenyl or alkynyl at the single end of the molecular chain (R2’ Furthermore, an organopolysiloxane with a silanol group at the other end of the molecular chain (in the case of n = 1 to 100 in formula (4)) undergoes a hydrosilylation addition reaction with a cyclic organohydrogen polysiloxane with hydrogen atoms bonded to silicon atoms as represented by the above formula (5) in the presence of a catalyst containing a platinum compound, so that the hydrogen atoms (SiH group) bonded to silicon atoms and aliphatic unsaturated monovalent hydrocarbon groups (R, alkenyl, alkynyl, etc.) are formed. 2’ Addition, forming a carbon-silicon bond (i.e., through the hydrogen atom (SiH group) bonded to the silicon atom in formula (2) above and the aliphatic unsaturated monovalent hydrocarbon group (R group) such as alkenyl or alkynyl in formula (3) above). 2’ The addition reaction of ), or the hydrogen atom (SiH group) bonded to silicon atoms in formula (5) above and the aliphatic unsaturated monovalent hydrocarbon group (R group) such as alkenyl or alkynyl in formula (4) above. 2’ The addition reaction of ) forms a divalent hydrocarbon group such as alkylene and / or alkenylene as represented by A in the above formula (1), thereby producing an organosilicon compound represented by the above formula (1).

[0076] In equations (3) and (4) above, R is used as... 2’ The aliphatic unsaturated monovalent hydrocarbon groups representing 2 to 12 carbon atoms can be listed as R in the above formula (1). 2 This is the same group exemplified as an aliphatic unsaturated monovalent hydrocarbon group with 2 to 12 carbon atoms. As R 2’ Preferred compounds include vinyl, allyl, and other alkenyl groups, with vinyl being particularly preferred.

[0077] As an organohydrosilane or organohydropolysiloxane represented by the above formula (2), specifically, the compounds shown below can be exemplified.

[0078] [Chemistry 11]

[0079]

[0080] (In the formula, n is the same as above.)

[0081] Specifically, the compounds shown below can be exemplified as cyclic organopolysiloxanes represented by the above formula (3).

[0082] [Chemistry 12]

[0083]

[0084] As an organosilane or organopolysiloxane represented by the above formula (4), specifically, the compounds shown below can be exemplified.

[0085] [Chemistry 13]

[0086]

[0087] (In the formula, n is the same as above.)

[0088] Specifically, the compounds shown below can be exemplified as cyclic organohydrogen polysiloxanes represented by the above formula (5).

[0089] [Chemistry 14]

[0090]

[0091] Regarding the reaction ratio of the organohydrosilane or organohydropolysiloxane represented by formula (2) to the cyclic organopolysiloxane represented by formula (3), considering the suppression of byproducts during the hydrosilylation addition reaction and the improvement of the storage stability and properties of the obtained organosilicon compound, the ratio of alkenyl, alkynyl and other aliphatic unsaturated monovalent hydrocarbon groups in the cyclic organopolysiloxane represented by formula (3) to 1 mol of silyl methyl ...

[0092] Furthermore, regarding the reaction ratio of the organosilane or organopolysiloxane represented by formula (4) to the cyclic organohydrogen polysiloxane represented by formula (5), considering the suppression of byproducts during the hydrosilylation addition reaction and the improvement of the storage stability and properties of the obtained organosilicon compound, the ratio of alkenyl, alkynyl, and other aliphatic unsaturated monovalent hydrocarbon groups in the organosilane or organopolysiloxane represented by formula (4) to 1 mol of silyl (SiH) in the cyclic organohydrogen polysiloxane represented by formula (5) is preferably 0.5 to 1.5 mol, and more preferably 0.7 to 1.4 mol.

[0093] There are no particular limitations on the catalysts containing platinum compounds used in the above-mentioned hydrosilylation addition reaction. Specific examples include chloroplatinic acid, alcoholic solutions of chloroplatinic acid, toluene or xylene solutions of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes, tetra(triphenylphosphine)platinum, dichlorobis(triphenylphosphine)platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, platinum-carbon, platinum-alumina, platinum-silica, and other supported catalysts. Among these, from the perspective of the position selectivity of the hydrosilylation addition reaction, toluene or xylene solutions of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes are preferred.

[0094] There is no particular limitation on the amount of catalyst containing platinum compounds used. From the perspective of reactivity and productivity, it is preferable that the amount of platinum atoms contained in 1 mol of organosilicon compounds or organopolysiloxane compounds with aliphatic unsaturated monovalent hydrocarbon groups such as alkenyl or alkynyl groups represented by the above formula (3) or (4) is 1 × 10⁻⁶. -7 ~1×10 -2 The amount of mol is more preferably 1 × 10⁻⁶. -7 ~1×10 -3 The amount in mol.

[0095] Furthermore, a co-catalyst can be used to improve the reactivity of the hydrosilylation addition reaction. While co-catalysts commonly used in hydrosilylation addition reactions can be used, in this invention, ammonium salts of inorganic acids, amide compounds, or carboxylic acids are preferred.

[0096] Specific examples of ammonium salts of inorganic acids include ammonium chloride, ammonium sulfate, ammonium aminosulfate, ammonium nitrate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium diphosphite, ammonium carbonate, ammonium bicarbonate, ammonium sulfide, ammonium borate, and ammonium borofluoride. Among these, ammonium carbonate and ammonium bicarbonate are preferred.

[0097] Specific examples of amide compounds include formamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, acrylamide, malondiamide, succinamide, maleamide, fumaramide, benzamide, phthalamide, palmitamide, stearamide, etc. Among these, formamide and stearamide are preferred, and formamide is more preferred.

[0098] Specific examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, lactic acid, glycolic acid, trifluoroacetic acid, maleic acid, fumaric acid, succinic acid, tartaric acid, and oxalic acid. Among these, formic acid, acetic acid, lactic acid, maleic acid, fumaric acid, succinic acid, and trifluoroacetic acid are preferred, and acetic acid and trifluoroacetic acid are more preferred.

[0099] There is no particular limitation on the amount of co-catalyst used. From the viewpoints of reactivity, position selectivity, and cost of the hydrosilylation addition reaction, 1 × 10⁻⁶ is preferred over 1 mol of organosilanes or organopolysiloxanes containing aliphatic unsaturated monovalent hydrocarbon groups such as alkenyl or alkynyl groups as represented by the above formula (3) or (4). -5 ~1×10 -1 mol, more preferably 1×10 -4 ~5×10 -1 mol.

[0100] Furthermore, while the aforementioned hydrosilylation addition reaction can proceed even without a solvent, it can also be carried out using a solvent. Specific examples of solvents that can be used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as N,N-dimethylformamide; and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents can be used individually or in combination.

[0101] There is no particular limitation on the amount of solvent used, but from the viewpoint of productivity such as production efficiency, it is preferable to use 0 to 1000 parts by mass, more preferably 0 to 300 parts by mass, relative to the total of 100 parts by mass of organosilane compounds or organopolysiloxane compounds having aliphatic unsaturated monovalent hydrocarbon groups such as alkenyl or alkynyl as represented by formula (3) or (4) above and organosilane compounds or organopolysiloxane compounds having hydrogen atoms bonded to silicon atoms as represented by formula (2) or (5) above.

[0102] The reaction temperature in the above-mentioned hydrosilylation addition reaction is not particularly limited and can be carried out at room temperature (23℃±15℃) to under heating, preferably room temperature (23℃±15℃) to 200℃. To obtain a suitable reaction rate, it is more preferable to carry out the reaction under heating; when carrying out the reaction under heating, the reaction temperature is more preferably 40 to 110℃, and even more preferably 40 to 90℃. Furthermore, the reaction time is not particularly limited, preferably 1 to 60 hours, more preferably 1 to 30 hours, and even more preferably 1 to 20 hours.

[0103] As a compound obtained in this way, represented by the above formula (1), compounds represented by the following formulas can be listed, but are not limited to these.

[0104] [Chemistry 15]

[0105]

[0106] (In the formula, k is an integer from 0 to 2, m is an integer from 3 to 6, k+m is an integer from 3 to 8, and n is an integer from 0 to 100.)

[0107] In addition, as specific examples of compounds obtained in this way and represented by the above formula (1), the following compounds can be listed, but are not limited to these.

[0108] [Chemistry 16]

[0109]

[0110] [Chemistry 17]

[0111]

[0112] <Additives>

[0113] In addition, the present invention provides an additive for a condensation-curing type room temperature curing resin composition comprising the above-mentioned organosilicon compound.

[0114] In condensation-curing room temperature curing organopolysiloxane compositions (e.g., condensation-curing room temperature curing organopolysiloxane (base polymer) containing a linear organopolysiloxane (base polymer) with two-terminated silanol groups or hydrolyzable silyl groups, a hydrolyzable organosilane compound (crosslinking agent), a condensation-curing catalyst, and a reinforcing filler), the organosilicon compounds of the present invention are suitable for use as additives (strength enhancers) to improve the strength of the cured product.

[0115] When the organosilicon compound of the present invention is used as a strength enhancer in a condensation-curing room temperature-curing resin composition, the amount added is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of the condensation-curing room temperature-curing resin composition.

[0116] The strength of the cured product of the condensation-curing room temperature curing resin composition containing the organosilicon compound of the present invention as an additive refers to hardness, tensile strength, and tensile shear bond strength, which can be measured according to JIS K-6249.

[0117] Example

[0118] The following examples and references illustrate the invention in more detail, but the invention is not limited to these examples. It should be noted that molecular weight represents the number-average molecular weight of polystyrene determined by GPC using toluene as the elution solvent.

[0119] Synthesis of organosilicon compounds

[0120] [Example 1]

[0121] Synthesis of organosilicon compound 1 (1)

[0122] In a 500 mL detachable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 34.4 g (0.1 mol, alkenyl content: 0.4 mol) of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and 0.15 g (platinum atomic weight: 6.8 × 10⁻⁶) platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were added. -650 g of toluene and 119.5 g of organopolysiloxane (SiH group: 0.4 mol), represented by formula (6), with hydrogen atoms (SiH group) bonded to silicon atoms at one end of the molecular chain and silanol group (hydroxyl group bonded to silicon atoms) at the other end, were added dropwise to the mixture. The mixture was heated and stirred at 80 °C for 3 hours. Gas chromatography was used to confirm that the peak of the organopolysiloxane with hydrogen atoms bonded to silicon atoms at one end of the molecular chain from the raw material had completely disappeared, and the reaction was considered to be complete. After the reaction was completed, the mixture was subjected to vacuum distillation (120 °C, 5 mmHg) for 2 hours, filtered, and 151.4 g of organosilicon compound 1 (number average molecular weight: 1571), represented by formula (7), was obtained.

[0123] [Chemistry 18]

[0124]

[0125] [Chemistry 19]

[0126]

[0127] [Example 2]

[0128] Synthesis of organosilicon compound 1 (2)

[0129] In a 500 mL detachable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 129.9 g (0.4 mol, alkenyl content: 0.4 mol) of an organopolysiloxane represented by the following formula (8), having a vinyl group at one end of the molecular chain and a silanol group (hydroxyl group bonded to a silicon atom) at the other end, and 0.15 g (platinum atomic weight: 6.8 × 10⁻⁶) of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were added. -6 50 g of toluene and 1,3,5,7-tetramethyl-1,3,5,7-tetrahydrocyclotetrasiloxane (SiH group amount: 0.4 mol) were added dropwise, and the mixture was heated and stirred at 80 °C for 3 hours. Gas chromatography was used to confirm that the peak of the alkenyl-containing organopolysiloxane from the raw material had completely disappeared, and the reaction was considered to be finished. After the reaction was completed, the mixture was subjected to vacuum distillation for 2 hours (120 °C, 5 mmHg), filtered, and 153.0 g of organosilicon compound 1 represented by the above formula (7) (number average molecular weight: 1571) was obtained.

[0130] [Chemistry 20]

[0131]

[0132] [Example 3]

[0133] Synthesis of organosilicon compound 2

[0134] In a 500 mL detachable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, 40.9 g (0.1 mol, alkenyl content: 0.4 mol) of vinyl(dimethyl)hydroxysilane (represented by formula (9) below) and 0.15 g (platinum atomic weight: 6.8 × 10⁻⁶) of a toluene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were added. -6 50 g of toluene and 1,3,5,7-tetramethyl-1,3,5,7-tetrahydrocyclotetrasiloxane (SiH group amount: 0.4 mol) were added and heated and stirred at 80 °C for 3 hours. Gas chromatography was used to confirm that the peak of the alkenyl-containing organopolysiloxane from the raw material had completely disappeared, and the reaction was considered to be finished. After the reaction was completed, vacuum distillation was carried out for 2 hours (120 °C, 5 mmHg), and the mixture was filtered to obtain 64.3 g of organosilicon compound 2 (number average molecular weight: 651) represented by the following formula (10).

[0135] [Chemistry 21]

[0136]

[0137] [Chemistry 22]

[0138]

[0139] The effects of the organosilicon compounds of the present invention will be explained in more detail using reference examples. Furthermore, the properties in the reference examples are values ​​at 23°C. "Parts" means "parts by mass". Viscosities are values ​​measured using a rotational viscometer at 23°C.

[0140] [Reference Example 1]

[0141] Composition 1 was prepared by adding 70 parts of linear dimethyl polysiloxane with a viscosity of 20000 mPa·s and silanol-terminated ends, 15 parts of linear dimethyl polysiloxane with a viscosity of 100 mPa·s and trimethylsilyl-terminated ends, 3 parts of organosilicon compound 1, and 10 parts of fumed silica, and mixing under reduced pressure for 30 minutes. Next, 5 parts of methyltris(methylethyl ketoxime)silane, 3 parts of vinyltris(methylethyl ketoxime)silane, 0.05 parts of dioctyltin dilaurate, and 1 part of 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBE-903) as an adhesion promoter, and mixing again under reduced pressure until homogeneous.

[0142] [Reference Example 2]

[0143] Composition 2 was prepared in the same manner as in Reference Example 1, except that 6 parts of organosilicon compound 1 were added.

[0144] [Reference Example 3]

[0145] Composition 3 was prepared in the same manner as in Reference Example 1, except that two parts of organosilicon compound 2 were added instead of organosilicon compound 1.

[0146] [Compare with Example 1]

[0147] Composition 4 was prepared in the same manner as in Reference Example 1, except that organosilicon compound 1 was not added.

[0148] (test)

[0149] [Physical Properties of Sheets]

[0150] The freshly prepared room-temperature curing resin compositions from Reference Examples 1-3 and Comparative Reference Example 1 were molded into sheets with a thickness of 2 mm and exposed to air at 23°C and 50% RH. The sheets were then left to stand in the same atmosphere for 7 days, and the physical properties (hardness, tensile strength) of the cured products were determined according to JIS K-6249. It should be noted that the hardness was measured using a Shore A hardness tester according to JIS K-6249. The results are shown in Table 1.

[0151] [Shear-bond test]

[0152] Using freshly prepared room-temperature curable resin compositions from Reference Examples 1-3 and Comparative Reference Example 1, and aluminum substrates measuring 25 mm wide and 100 mm long, the substrates were cured at 23°C and 50% RH for 7 days to produce adhesive surfaces with a bonding area of ​​2.5 mm. 2 Shear bond strength was determined for a 1 mm thick bond specimen according to JIS K-6249. The results are shown in Table 1.

[0153] [Table 1]

[0154] Reference Example 1 See Example 2 See Example 3 Compare with Example 1 Composition 1 Composition 2 Composition 3 Composition 4 Type A hardness 34 35 35 29 Tensile strength (MPa) 2.2 2.4 2.4 1.6 Shear bond strength (MPa) 1.8 2.0 2.0 1.3

[0155] As can be seen from the results in Table 1, the cured products of the room temperature curing organopolysiloxane compositions (compositions 1 to 3) containing organosilicon compounds 1 and 2 of the present invention, manufactured in Reference Examples 1 to 3, have higher tensile strength and shear bond strength compared with the cured product of the room temperature curing organopolysiloxane composition (composition 4) without organosilicon compounds of the present invention manufactured in Comparative Reference Example 1.

Claims

1. An organosilicon compound represented by the following formula (1), [Chemistry 1] In the formula, R 1 R is a monovalent hydrocarbon group consisting of 1 to 12 unsubstituted or substituted carbon atoms, excluding aliphatic unsaturated bonds. 2 R is a hydrogen atom or an aliphatic unsaturated monovalent hydrocarbon group with 2 to 12 carbon atoms. 3 A is a monovalent hydrocarbon group with 1 to 12 carbon atoms that is unsubstituted or substituted and does not contain aliphatic unsaturated bonds; A is a divalent hydrocarbon group with 2 to 8 carbon atoms; k is an integer from 0 to 2; m is an integer from 3 to 6; k+m is an integer from 3 to 8; and n is an integer from 0 to 100.

2. The organosilicon compound according to claim 1, which is an additive used to improve the cured strength of a condensation-curing room temperature curing resin composition.

3. A method for manufacturing an organosilicon compound according to claim 1 or 2, comprising the step of carrying out a hydrosilylation addition reaction of an organohydrosilane or organohydropolysiloxane represented by formula (2) with a cyclic organopolysiloxane represented by formula (3) in the presence of a catalyst containing a platinum compound. [Chemistry 2] In the formula, R 3 It refers to a monovalent hydrocarbon group with 1 to 12 unsubstituted or substituted carbon atoms (excluding aliphatic unsaturated bonds), where n is an integer from 0 to 100. [Chemistry 3] In the formula, R 1 R is a monovalent hydrocarbon group consisting of 1 to 12 unsubstituted or substituted carbon atoms, excluding aliphatic unsaturated bonds. 2’ It is an aliphatic unsaturated monovalent hydrocarbon group with 2 to 12 carbon atoms, where k is an integer from 0 to 2, m is an integer from 3 to 6, and k+m is an integer from 3 to 8.

4. A method for manufacturing an organosilicon compound according to claim 1 or 2, comprising the step of carrying out a hydrosilylation addition reaction of an organosilane or organopolysiloxane represented by formula (4) with a cyclic organohydropolysiloxane represented by formula (5) in the presence of a catalyst containing a platinum compound. [Chemistry 4] In the formula, R 2’ R is an aliphatic unsaturated monovalent hydrocarbon group with 2 to 12 carbon atoms. 3 It refers to a monovalent hydrocarbon group with 1 to 12 unsubstituted or substituted carbon atoms (excluding aliphatic unsaturated bonds), where n is an integer from 0 to 100. [Chemistry 5] In the formula, R 1 It is a monovalent hydrocarbon group with 1 to 12 unsubstituted or substituted carbon atoms, excluding aliphatic unsaturated bonds, where k is an integer from 0 to 2, m is an integer from 3 to 6, and k+m is an integer from 3 to 8.

5. An additive for use in condensation-curing room-temperature curing resin compositions, comprising the organosilicon compound according to claim 1 or 2.

6. The additive according to claim 5, wherein, The condensation-curing room temperature curing resin composition is a condensation-curing room temperature curing organopolysiloxane composition.

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