thermosetting components

Abstract

The present invention provides a thermosetting composition comprising a polyorganosiloxane having an alkenyl group having 2 to 40 carbon atoms bonded to silicon atoms, a polyorganosiloxane having a Si-H group, a platinum group metal catalyst, and a crosslinking inhibitor; The crosslinking inhibitor contains at least one of the compounds represented by formula (1) and the compounds represented by formula (2). (In equation (1), R) 1~R The 8 series represents hydrogen atoms or specific functional groups, etc. (In equation (2), R) 11~R The 13 series separately represents hydrocarbon groups that can have substituents.

Description

Technical Field

[0001] This invention relates to a thermosetting composition. Prior Technology

[0002] The main hardening reaction in the field of silicone is the hydrosilicification reaction, which is also known as a complex addition reaction. The silane hydrotreating reaction is a reaction between a compound having at least one unsaturated group and a compound having at least one hydrogen atom bonded to a silicon atom. This reaction is represented, for example, by reaction formula (I) when the unsaturated group is alkene-type and by reaction formula (II) when the unsaturated group is alkyne-type. [Chemistry 1]

[0003] The hydrosiliconization reaction is typically carried out using a catalyst. A suitable catalyst for this reaction is a platinum catalyst (e.g., Karstedt's catalyst) (see, for example, Patent Document 1). With this catalyst, the hydrosiliconization reaction can be carried out at a rapid reaction rate of about a few minutes at room temperature.

[0004] Generally, thermosetting compositions must be transported, stored, and used within the required time before curing. On the other hand, the hydrosiliconization reaction using a platinum catalyst, as mentioned above, proceeds rapidly at room temperature, taking only a few minutes. Therefore, thermosetting compositions utilizing hydrosiliconization reactions are often used in conjunction with crosslinking inhibitors that can temporarily suppress the hydrosiliconization reaction. For example, it has been proposed to use an acetylene inhibitor as a crosslinking inhibitor in thermosetting polyorganosiloxane compositions that utilize a hydrosilicification reaction carried out with a platinum catalyst (for example, see Patent Document 2). As acetylene inhibitors, alkyne alcohols such as 1,1-diphenyl-2-propyn-1-ol have been used in recent years (for example, see Patent Document 3). [Patent Literature]

[0005] [Patent Document 1] U.S. Patent No. 3,775,452 [Patent Document 2] U.S. Patent No. 3,445,420 [Patent Document 3] Japanese Patent Publication No. 2014-523938 Summary of the Invention

[0006] [The technical problem that the invention aims to solve]

[0007] In the present invention, when 1,1-diphenyl-2-propyn-1-ol is used as a crosslinking inhibitor in thermosetting polyorganosiloxane compositions (also referred to as "thermosetting silicone compositions"), the curing start temperature is, for example, 118°C (see Comparative Example 1 of this specification). Thermosetting silicone compositions utilizing hydrogenation reactions are widely used in various silicone materials, such as silicone rubber foams, silicone rubber molds (silicone rubber for molding), silicone encapsulation materials, and silicone adhesives. In such cases, the required curing initiation temperature varies depending on the application of the thermosetting silicone composition. Furthermore, a higher curing initiation temperature is ideal depending on the application. Therefore, it is desirable to have a thermosetting silicone composition with a higher curing initiation temperature than when using 1,1-diphenyl-2-propyn-1-ol as a crosslinking inhibitor.

[0008] The present invention is made in view of the foregoing circumstances and aims to provide a thermosetting composition with a higher curing initiation temperature than when 1,1-diphenyl-2-propyn-1-ol is used as a crosslinking inhibitor. [Technical means]

[0009] After conducting in-depth research to solve the aforementioned problems, the inventors discovered that the aforementioned problems could be solved and completed the present invention with the following key points.

[0010] That is, the present invention includes the following. [1] A thermosetting composition comprising a polyorganosiloxane having an alkenyl group having 2 to 40 carbon atoms bonded to silicon atoms, a polyorganosiloxane having a Si-H group, a platinum group metal catalyst, and a crosslinking inhibitor; Furthermore, the aforementioned crosslinking inhibitor contains at least one of the compounds represented by formula (1) and the compounds represented by formula (2). [Chemistry 2] (In the aforementioned formula (1), R1 and R2 independently represent hydrogen atoms or alkyl groups that may have substituents; or, R1 and R2 together form an aromatic hydrocarbon ring that may have alkyl groups and that alkyl group may have substituents, or form -O-; R3 and R4 series respectively represent hydrogen atoms or alkyl groups that may have substituents; R5 and R6 series respectively represent hydrogen atoms or alkyl groups that may have substituents; The R7 and R8 series each independently represent a hydrogen atom; However, R5 and R7 may also differ from the above definition, together forming an aromatic hydrocarbon ring that may have an alkyl group and that alkyl group may have substituents; However, R6 and R8 may also differ from the above definition, together forming an aromatic hydrocarbon ring that may have an alkyl group and that alkyl group may have substituents; However, when R1 and R2 do not form -O- together, the compound represented by the aforementioned formula (1) has at least one alkyl group that may have substituents. [Chemistry 3] (In the aforementioned formula (2), R11 to R13 each independently represent hydrocarbon groups that may have substituents). [2] The thermosetting composition as described in item [1], wherein the aforementioned crosslinking inhibitor contains a compound represented by the aforementioned formula (1). [3] The thermosetting composition as described in item [1] or [2], wherein in the aforementioned formula (1), R1, R2, R7, and R8 represent hydrogen atoms; R3 to R6 satisfy either (I) or (II) below: (I): R3 and R5 series independently represent alkyl groups; R4 and R6 represent hydrogen atoms; (II): R3 and R5 represent hydrogen atoms; R4 and R6 each represent alkyl groups independently. [4] The thermosetting composition as described in any of [1] to [3], wherein the carbon number of the alkyl group in the aforementioned formula (1) is 1 to 12 respectively. [5] The thermosetting composition as described in item [1], wherein the aforementioned crosslinking inhibitor contains a compound represented by the aforementioned formula (2). [6] The thermosetting composition as described in item [1] or [5], wherein in the aforementioned formula (2), R 11 to R 13 respectively represent alkyl groups that may have substituents or phenyl groups that may have substituents. [7] The thermosetting composition as described in item [6], wherein the carbon number of the alkyl group in the aforementioned formula (2) is 1 to 12 respectively. [Effects of the Invention]

[0011] According to the present invention, a thermosetting composition is provided that has a higher curing initiation temperature than when 1,1-diphenyl-2-propyn-1-ol is used as a crosslinking inhibitor. Implementation

[0012] (Thermosetting composition) The thermosetting composition of the present invention contains at least a polyorganosiloxane (a1), a polyorganosiloxane (a2), a platinum group metal catalyst (A2), and a crosslinking inhibitor (A3), and may further contain other components as required.

[0013] <Polyorganosiloxanes (a1) and (a2)> Polyorganosiloxanes (a1) are polyorganosiloxanes having an alkenyl group with 2 to 40 carbon atoms bonded to silicon atoms. Polyorganosiloxanes (a2) are polyorganosiloxanes with Si-H groups. Therefore, alkenyl groups with 2 to 40 carbon atoms can also be substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, and heteroaryl groups. An example of a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to silicon atoms is a polyorganosiloxane (a1') containing one or more units selected from the group consisting of siloxane units represented by SiO2 (Q' unit), siloxane units represented by R1'R2'R3'SiO1 / 2 (M' unit), siloxane units represented by R4'R5'SiO2 / 2 (D' unit), and siloxane units represented by R6'SiO3 / 2 (T' unit), and containing at least one unit selected from the group consisting of M' unit, D' unit, and T' unit. An example of a Si-H-based polyorganosiloxane (a2) is a polyorganosiloxane (a2') containing one or more units selected from the group consisting of siloxane units represented by SiO2 (Q" unit), siloxane units represented by R1"R2"R3"SiO1 / 2 (M" unit), siloxane units represented by R4"R5"SiO2 / 2 (D" unit), and siloxane units represented by R6"SiO3 / 2 (T" unit), and containing at least one unit selected from the group consisting of M" unit, D" unit, and T" unit.

[0014] R1' to R6' are groups bonded to silicon atoms, and each independently represents a substituted alkyl or substituted alkenyl group, except that at least one of R1' to R6' is a substituted alkenyl group. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0015] R1” to R6” are groups or atoms bonded to silicon atoms, and each independently represents a substituted alkyl group or hydrogen atom, except that at least one of R1” to R6” is a hydrogen atom. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0016] Alkyl groups can be straight-chain, branched, or cyclic, but ideally they are straight-chain or branched alkyl groups; although there is no particular limitation on their carbon number, they are usually 1 to 40, ideally less than 30, more ideally less than 20, and even more ideally less than 10.

[0017] Specific examples of substituted linear or branched alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1- Dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., but not limited to these; its carbon number is usually 1 to 14, ideally 1 to 10, and more ideally 1 to 6. Among them, the methyl group is particularly ideal.

[0018] Specific examples of substituted cyclic alkyl groups include: cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl... Cycloalkyl groups such as butyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, etc.; bicycloalkyl groups such as bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl, etc., but not limited to these; the number of carbon atoms is usually 3 to 14, ideally 4 to 10, and more ideally 5 to 6.

[0019] Alkenyl groups can be either linear or branched; their carbon number, while not particularly limited, is usually 2 to 40, ideally below 30, even more ideally below 20, and even more ideally below 10.

[0020] Specific examples of substituted linear or branched alkenyl groups include, but are not limited to, vinyl, allyl, butenyl, and pentenyl; their carbon number is usually 2 to 14, ideally 2 to 10, and more ideally 1 to 6. Vinyl and 2-propenyl are particularly ideal. Specific examples of substituted cyclic alkenyl groups include cyclopentenyl, cyclohexenyl, etc., but are not limited to these; their carbon number is usually 4 to 14, ideally 5 to 10, and more ideally 5 to 6.

[0021] Polyorganosiloxanes (a1') contain one or more units selected from the group consisting of Q', M', D', and T' units, and contain at least one unit selected from the group consisting of M', D', and T' units. Two or more polyorganosiloxanes satisfying these conditions can also be used in combination as polyorganosiloxanes (a1').

[0022] Ideal combinations selected from two or more of the groups of Q', M', D' and T' units can be listed as: (Q' unit and M' unit), (D' unit and M' unit), (T' unit and M' unit), (Q' unit, T' unit and M' unit), but are not limited to these.

[0023] Furthermore, when the polyorganosiloxane contained in two or more polyorganosiloxanes (a1') is present, the combination of (Q' unit and M' unit) and (D' unit and M' unit), the combination of (T' unit and M' unit) and (D' unit and M' unit), and the combination of (Q' unit and T' unit and M' unit) and (T' unit and M' unit) are ideal, but not limited to these combinations.

[0024] The polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q" units, M" units, D" units and T" units, and contains at least one unit selected from the group consisting of M" units, D" units and T" units. As a polyorganosiloxane (a2'), two or more polyorganosiloxanes that satisfy the foregoing conditions can also be used in combination.

[0025] Ideal combinations selected from two or more of the groups of Q” units, M” units, D” units and T” units can be listed as: (M” units and D” units), (Q” units and M” units), (Q” units and T” units and M” units), but are not limited to these.

[0026] Polyorganosiloxanes (a1') are composed of siloxane units whose silicon atoms are bonded to alkyl and / or alkenyl groups. The proportion of alkenyl groups in all substituents represented by R1' to R6' is ideally 0.1 to 50.0 mol%, more ideally 0.5 to 30.0 mol%, and the remaining R1' to R6' can be alkyl groups.

[0027] Polyorganosiloxanes (a2') are composed of siloxane units bonded to silicon atoms and alkyl and / or hydrogen atoms. The proportion of hydrogen atoms in all substituents, represented by R1” to R6”, is ideally 0.1 to 50.0 mol%, more ideally 10.0 to 40.0 mol%, with the remainder R1” to R6” being alkyl groups.

[0028] The weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000. From the viewpoint of achieving the effects of the present invention with good reproducibility, it is ideally 5,000 to 50,000. Furthermore, in this invention, the determination of the weight average molecular weight, number average molecular weight, and dispersity of polyorganosiloxanes can be performed, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation). The column temperature is set to 40°C, tetrahydrofuran is used as the dissolution solution, the flow rate is set to 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko Corporation) is used as the standard sample.

[0029] While there is no particular limitation on the viscosity of the polyorganosiloxane (a1) and polyorganosiloxane (a2), they are typically 10 to 1,000,000 mPa·s, respectively. From the viewpoint of achieving the effects of the present invention with good reproducibility, they are ideally 50 to 10,000 mPa·s, respectively. Furthermore, the viscosity of the polyorganosiloxane (a1) and polyorganosiloxane (a2) is the value measured at 25°C using an E-type rotational viscometer.

[0030] Polyorganosiloxanes (a1) and (a2) are formed by reacting with each other through a hydrosilicification reaction. Therefore, their curing mechanism is different from that of silanol groups, for example. Thus, neither of the siloxanes needs to contain silanol groups or form silanol groups through hydrolysis like alkoxy groups.

[0031] For thermosetting compositions, the molar ratio (alkenyl group: hydrogen atom constituting Si-H bond) between the alkenyl group contained in polyorganosiloxane (a1) and the hydrogen atom constituting Si-H bond contained in polyorganosiloxane (a2) is ideally in the range of 1.0:0.5 to 1.0:0.66.

[0032] <Platinum Group Metal Catalyst (A2)> Platinum group metal catalysts (A2) are metal catalysts belonging to the platinum group. This platinum-based metal catalyst is used to promote the hydrosilicification reaction between the alkenyl group of polyorganosiloxane (a1) and the Si-H group of polyorganosiloxane (a2).

[0033] As a specific example of a platinum group metal catalyst, a known platinum group compound (platinum or a platinum-containing compound) can be used. Specific examples include: platinum micro powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid and dienes, platinum-olefin complexes, platinum-carbonyl complexes (platinum bis(acetylacetic acid), platinum bis(acetylacetone), etc.), chloroplatinic acid-alkenyl silicate complexes (chloroplatinic acid-divinyltetramethyldisiloxane complex, chloroplatinic acid-tetravinyltetramethylcyclotetrasiloxane complex, etc.), platinum-alkenyl silicate complexes (platinum-divinyltetramethyldisiloxane complex, platinum-tetravinyltetramethylcyclotetrasiloxane complex, etc.), and complexes of chloroplatinic acid and alkynyl alcohols. Among these, platinum-alkenyl silicate complexes are particularly ideal due to their high promoting effect on the hydrosilylation reaction. For these hydrogenation reactions, a single catalyst can be used, or two or more catalysts can be used in combination.

[0034] While not particularly limited, the alkenyl silicate used in platinum-alkenyl silicate complexes may include, for example, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane; alkenyl silicate oligomers in which a portion of the methyl group of such alkenyl silicate is replaced by ethyl, phenyl, or the like; and alkenyl silicate oligomers in which the vinyl group of such alkenyl silicate is replaced by allyl, hexenyl, or the like. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is ideal due to the good stability of the resulting platinum-alkenyl silicate complex.

[0035] The content of platinum group metal catalyst (A2) in thermosetting components is not particularly limited, but is generally in the range of 1.0 to 50.0 ppm relative to the total mass of polyorganosiloxane (a1) and polyorganosiloxane (a2).

[0036] <Cross-linking inhibitor (A3)> The crosslinking inhibitor (A3) contained in the thermosetting composition of the present invention is at least one of the compounds represented by formula (1) and the compounds represented by formula (2). The crosslinking inhibitor (A3), by containing at least one of the compounds represented by formula (1) and formula (2), can increase the curing start temperature of the thermosetting composition utilizing the hydrosilicification reaction compared to the use of 1,1-diphenyl-2-propyn-1-ol. The inventors hypothesize that, in thermosetting compositions, using at least one of the compounds represented by formula (1) and formula (2) as crosslinking inhibitors will result in a higher curing start temperature than when using 1,1-diphenyl-2-propyn-1-ol, because the compounds represented by formula (1) and formula (2) have a higher coordination ability for platinum group metal catalysts than 1,1-diphenyl-2-propyn-1-ol.

[0037] [Chemistry 4]

[0038] In formula (1), R1 and R2 represent hydrogen atoms or alkyl groups that may have substituents, respectively; or, R1 and R2 together form an aromatic hydrocarbon ring that may have alkyl groups and the aforementioned alkyl groups may have substituents, or form -O-. The R3 and R4 series respectively represent hydrogen atoms or alkyl groups that may have substituents. R5 and R6 series respectively represent hydrogen atoms or alkyl groups that may have substituents. The R7 and R8 series represent hydrogen atoms independently. However, R5 and R7 may also differ from the above definition, together forming an aromatic hydrocarbon ring that may have alkyl groups and the aforementioned alkyl groups may have substituents. However, R6 and R8 may also differ from the above definition, together forming an aromatic hydrocarbon ring that may have alkyl groups and the aforementioned alkyl groups may have substituents. However, when R1 and R2 do not form -O- together, the compound represented by formula (1) has at least one alkyl group that can have substituents.

[0039] The number of carbon atoms of the alkyl group in formula (1) is not particularly limited, but can be 1 to 12, for example. The alkyl group in formula (1) can be linear or branched. Examples of alkyl groups in formula (1) include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tributyl, pentyl, hexyl, octyl, nonyl, etc. Examples of substituents for alkyl groups in formula (1) include: halogen atoms, alkoxy groups, acetyl groups, hydroxyl groups, carboxyl groups, amino groups, imino groups, cyano groups, phenyl groups, thiols, sulfonic acid groups, nitro groups, aryl groups, heteroaryl groups, etc. Examples of alkoxy groups include: alkoxy groups having 1 to 6 carbon atoms. Examples of acetyl groups include: acetyl groups having 2 to 7 carbon atoms.

[0040] Examples of aromatic hydrocarbon rings formed by R1 and R2 together include the benzene ring. Examples of aromatic hydrocarbon rings formed by R5 and R7 together include the benzene ring. Examples of aromatic hydrocarbon rings formed by R6 and R8 together include the benzene ring.

[0041] In equation (1), R1, R2, R7 and R8 represent hydrogen atoms; R3 to R6 ideally satisfy either (I) or (II) below. (I): R3 and R5 series independently represent alkyl groups; R4 and R6 represent hydrogen atoms. (II): R3 and R5 represent hydrogen atoms; R4 and R6 each represent alkyl groups independently.

[0042] For example, R2 and R4 are both hydrogen atoms or the same group. For example, the R5 and R6 series are both hydrogen atoms or the same group. For example, when R5 and R7 together form an aromatic hydrocarbon ring that may have an alkyl group and that alkyl group may have substituents, R6 and R8 form the same aromatic hydrocarbon ring.

[0043] Examples of compounds represented by formula (1) include compounds represented by formula (1-1), compounds represented by formula (1-2), compounds represented by formula (1-3), and compounds represented by formula (1-4). Among these, from the viewpoint that the curing initiation temperature of the thermosetting composition is higher, the compounds represented by formula (1-1) and the compounds represented by formula (1-2) are ideal.

[0044] [Chemistry 5] In formula (1-1), R1 to R6 represent hydrogen atoms or alkyl groups that may have substituents. However, compounds represented by formula (1-1) have at least one alkyl group that may have substituents. In formula (1-2), R1 to R4 each independently represent a hydrogen atom or an alkyl group that may have substituents. R21 and R22 each independently represent an alkyl group that may have substituents. m and n each independently represent integers from 0 to 4. When m is 2 or more, the complex R21s may be the same or different. When n is 2 or more, the complex R22s may be the same or different. However, the compound represented by formula (1-2) has at least one alkyl group that may have substituents. In formulas (1-3), R3 to R6 each independently represent a hydrogen atom or an alkyl group that may have substituents. In formulas (1-4), R3 to R6 each independently represent a hydrogen atom or an alkyl group that may have substituents. R23 represents an alkyl group that may have substituents. n represents an integer from 0 to 2. When n is 2, the complex R23s may be the same or different. However, compounds represented by formulas (1-4) have at least one alkyl group that may have substituents.

[0045] [Chemistry 6]

[0046] (In formula (2), R11 to R13 each represent a hydrocarbon group that can have substituents.) Also, P represents a phosphorus atom.

[0047] For example, R11 to R13 each independently represent an alkyl group that may have substituents, or a phenyl group that may have substituents.

[0048] The number of carbon atoms in the alkyl group that may have substituents among R11 to R13 is not particularly limited, but can be listed as 1 to 12, respectively. Alkyl groups can be linear or branched. Examples of alkyl groups include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tributyl, pentyl, hexyl, octyl, nonyl, etc.

[0049] Examples of substituents that can be substituted for hydrocarbon groups among R11 to R13 include: halogen atoms, alkoxy groups, acetyl groups, hydroxyl groups, carboxyl groups, amino groups, imino groups, cyano groups, phenyl groups, thiols, sulfonic acid groups, nitro groups, aryl groups, heteroaryl groups, etc. Examples of alkoxy groups include alkoxy groups with 1 to 6 carbon atoms. Examples of acetyl groups include acetyl groups with 2 to 7 carbon atoms.

[0050] For example, R11 to R13 are the same group.

[0051] The content of at least one of the compounds represented by formula (1) and formula (2) in the thermosetting composition is not particularly limited, but from the viewpoint of achieving the effects of the present invention with good reproducibility, it is ideally 0.01 to 10% by mass relative to the non-volatile components, and more ideally 0.1 to 0.5% by mass.

[0052] <Other Ingredients> Other components, though not specifically limited, include, for example, solvents and stripping agents.

[0053] <<Solvent>> Thermosetting components may contain solvents for purposes such as adjusting viscosity. Examples of such solvents include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc., but are not limited to these.

[0054] More specifically, examples of solvents include: hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthol, limonene, toluene, xylene, symmetrical trimethylbenzene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc., but are not limited to these. Such solvents can be used alone or in combination of two or more.

[0055] When a thermosetting composition contains a solvent, its content is appropriately determined by taking into account the required viscosity of the composition, the coating method used, and the film thickness to be produced. However, relative to the overall composition, it is in the range of about 10 to 90% by mass.

[0056] <<Exfoliating Agent Ingredients>> The thermosetting composition of the present invention may contain a stripping agent. Because the thermosetting composition contains a release agent, when using the thermosetting composition as a peelable adhesive composition, the obtained adhesive layer can be peeled off in a reproducible and appropriate manner. As a stripping agent component, typical examples include non-curing polyorganosiloxanes. Specific examples include: polyorganosiloxanes containing epoxy groups, polyorganosiloxanes containing methyl groups, polyorganosiloxanes containing phenyl groups, etc., but are not limited to these. In this specification, "non-hardening" means that no hydrosiliconization reaction will occur. Furthermore, polydimethylsiloxane can be listed as a stripping agent component. This polydimethylsiloxane can also be modified. Examples of modifiable polydimethylsiloxanes include, but are not limited to, epoxy-containing polydimethylsiloxanes, unmodified polydimethylsiloxanes, and phenyl-containing polydimethylsiloxanes.

[0057] Ideal examples of polyorganosiloxanes as stripping agent components include, but are not limited to, epoxy-containing polyorganosiloxanes, methyl-containing polyorganosiloxanes, and phenyl-containing polyorganosiloxanes.

[0058] The weight-average molecular weight of the polyorganosiloxane used as a stripping agent is not particularly limited, but is typically 100,000 to 2,000,000, ideally 200,000 to 1,200,000, and more ideally 300,000 to 900,000. Furthermore, its dispersibility is not particularly limited, but is typically 1.0 to 10.0, and from the viewpoint of achieving proper stripping with good reproducibility, is ideally 1.5 to 5.0, and more ideally 2.0 to 3.0. The weight-average molecular weight and dispersibility can be determined by the methods described above related to polyorganosiloxanes. The viscosity of polyorganosiloxanes used as release agents is not particularly limited, but is typically 1,000 to 2,000,000 mm² / s. Furthermore, the viscosity value of polyorganosiloxanes used as release agents is expressed as kinematic viscosity, centistokes (cSt) = mm² / s. It can also be obtained by dividing viscosity (mPa·s) by density (g / cm³). That is, its value can be obtained from the viscosity and density measured at 25°C using an E-type rotational viscometer, and can be calculated using the formula: kinematic viscosity (mm² / s) = viscosity (mPa·s) / density (g / cm³).

[0059] Examples of epoxy-containing polyorganosiloxanes include those containing siloxane units (D10 units) represented by R111R112SiO2 / 2.

[0060] R111 refers to groups bonded to silicon atoms, representing alkyl groups; R112 refers to groups bonded to silicon atoms, representing epoxy groups or epoxy-containing organic groups; specific examples of alkyl groups can be listed above related to R1' to R6'. The epoxy group in an organic group containing an epoxy group can be an independent epoxy group that does not undergo condensation reaction with other rings, or it can be an epoxy group, such as 1,2-epoxycyclohexyl, that forms a condensation ring with other rings. Specific examples of epoxy-containing organic groups include 3-epoxypropoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl, but are not limited to these. An ideal example of an epoxy-containing polyorganosiloxane is an epoxy-containing polydimethylsiloxane, but it is not limited thereto.

[0061] Polyorganosiloxanes containing epoxy groups are those containing the aforementioned siloxane units (D 10 units), but may also contain Q units, M units and / or T units in addition to D 10 units. Specific examples of epoxy-containing polyorganosiloxanes include: polyorganosiloxanes composed only of D10 units, polyorganosiloxanes containing D10 units and Q units, polyorganosiloxanes containing D10 units and M units, polyorganosiloxanes containing D10 units and T units, polyorganosiloxanes containing D10 units, Q units and M units, polyorganosiloxanes containing D10 units, M units and T units, and polyorganosiloxanes containing D10 units, Q units, M units and T units, etc.

[0062] The ideal type of epoxy-containing polyorganosiloxane is polydimethylsiloxane containing epoxy groups with an epoxy value of 0.1 to 5. In addition, although there is no particular limitation on its weight average molecular weight, it is usually 1,500 to 500,000, and from the viewpoint of suppressing precipitation in the composition, it is ideally below 100,000.

[0063] Specific examples of epoxy-containing polyorganosiloxanes can be listed by formulas (E1) to (E3), but are not limited to these.

[0064] [Chemistry 7] (m1 and n1 represent the number of each repeating unit, and are positive integers.)

[0065] [Chemistry 8] (m2 and n2 represent the number of repeating units and are positive integers; R represents alkyl groups with 1 to 10 carbon atoms.)

[0066] [Chemistry 9] (m3, n3, and o3 represent the number of repeating units and are positive integers; R refers to alkyl groups with 1 to 10 carbon atoms.)

[0067] Examples of methyl-containing polyorganosiloxanes include those containing siloxane units (D 200 units) represented by R 210R 220SiO 2 / 2, and ideally those containing siloxane units (D 20 units) represented by R 221R 221SiO 2 / 2.

[0068] R 210 and R 220 are groups bonded to silicon atoms, each representing an alkyl group independently, except that at least one of them is methyl. The above examples are specific examples of alkyl groups. R 221 is a group bonded to a silicon atom, representing an alkyl group. Specific examples of alkyl groups can be listed above. Among them, methyl is ideal as R 221. As an ideal example of a methyl-containing polyorganosiloxane, polydimethylsiloxane can be cited, but is not limited thereto.

[0069] Methyl-containing polyorganosiloxanes are those containing the aforementioned siloxane units (D 200 units or D 20 units), but may also contain Q units, M units and / or T units in addition to D 200 units and D 20 units.

[0070] In a certain state, specific examples of methyl-containing polyorganosiloxanes can be listed as follows: polyorganosiloxanes composed only of D200 units, polyorganosiloxanes containing D200 units and Q units, polyorganosiloxanes containing D200 units and M units, polyorganosiloxanes containing D200 units and T units, polyorganosiloxanes containing D200 units, Q units and M units, polyorganosiloxanes containing D200 units, M units and T units, and polyorganosiloxanes containing D200 units, Q units, M units and T units.

[0071] Specific examples of methyl-containing polyorganosiloxanes include: polyorganosiloxanes composed solely of D20 units, polyorganosiloxanes containing D20 units and Q units, polyorganosiloxanes containing D20 units and M units, polyorganosiloxanes containing D20 units and T units, polyorganosiloxanes containing D20 units, Q units, and M units, polyorganosiloxanes containing D20 units, M units, and T units, and polyorganosiloxanes containing D20 units, Q units, M units, and T units.

[0072] Specific examples of methyl-containing polyorganosiloxanes can be listed, but are not limited to those represented by formula (M1).

[0073] [Chemistry 10] (n 4 represents the number of repeating units and is a positive integer.)

[0074] Examples of phenyl-containing polyorganosiloxanes include those containing siloxane units (D 30 units) denoted as R 31R 32SiO 2 / 2.

[0075] R 31 refers to groups bonded to silicon atoms, representing phenyl or alkyl groups; R 32 refers to groups bonded to silicon atoms, representing phenyl groups; specific examples of alkyl groups can be listed above, but methyl is ideal.

[0076] The phenyl-containing polyorganosiloxane is one containing the aforementioned siloxane unit (D 30 unit), but may also contain Q unit, M unit and / or T unit in addition to D 30 unit.

[0077] Specific examples of phenyl-containing polyorganosiloxanes include polyorganosiloxanes composed solely of D30 units, polyorganosiloxanes containing D30 and Q units, polyorganosiloxanes containing D30 and M units, polyorganosiloxanes containing D30 and T units, polyorganosiloxanes containing D30, Q, and M units, polyorganosiloxanes containing D30, M, and T units, and polyorganosiloxanes containing D30, Q, M, and T units.

[0078] Specific examples of phenyl-containing polyorganosiloxanes may be represented by formulas (P1) or (P2), but are not limited to these.

[0079] [Chemistry 11] (m5 and n5 represent the number of repeating units and are positive integers.)

[0080] [Chemistry 12] (m6 and n6 represent the number of repeating units, and are positive integers.)

[0081] Polyorganosiloxanes used as stripping agents can be commercially available products or synthetic compounds. Commercially available polyorganosiloxanes include, for example: Wacker Chemie's WACKERSILICONE FLUID AK series (AK50, AK350, AK1000, AK10000, AK1000000) or GENIOPLAST GUM; Shin-Etsu Chemical Co., Ltd.'s dimethyl silicone oil (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968) and cyclic dimethyl silicone oil (KF-995); Gelest's epoxy-containing polyorganosiloxanes (trade names CMS-227, ECMS-327); and Shin-Etsu Chemical Co., Ltd.'s epoxy-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, X-2). 2-343); epoxy-containing polyorganosiloxanes manufactured by Dow Corning (BY16-839); phenyl-containing polyorganosiloxanes manufactured by Gelest (PMM-1043, PMM-1025, PDM-0421, PDM-0821); phenyl-containing polyorganosiloxanes manufactured by Shin-Etsu Chemical Co., Ltd. (KF50-3000CS); phenyl-containing polyorganosiloxanes manufactured by Momentive (TSF431, TSF433), etc., but not limited to these.

[0082] There is no particular limitation on the content of the stripping agent component in thermosetting compositions.

[0083] While there is no particular limitation on the viscosity of thermosetting components, it is typically 500~20,000 mPa·s at 25°C, with an ideal range of 1,000~5,000 mPa·s. The viscosity of thermosetting components can be adjusted by considering various factors such as the coating method used, the required film thickness, and by changing the type of solvent used or its ratio, as well as the concentration of film components.

[0084] For the purpose of removing foreign matter, the solvents or solutions used can be filtered using filters during the manufacturing process of thermosetting compositions or after mixing all the components.

[0085] The use of the thermosetting composition of the present invention is not particularly limited, and can be used for all known thermosetting silicone compositions, such as silicone rubber foam, silicone rubber mold (silicone rubber for molding), silicone encapsulation materials, silicone adhesives and various silicone materials. [Example]

[0086] The present invention will be described in more detail below with examples, but the present invention is not limited to the examples described below. Furthermore, the apparatus used is as follows.

[0087] [device] (1) Mixer: ARE-500 self-rotating and revolution-rotating mixer manufactured by Shin-Ki Corporation. (2) Rheometer: Anton Paar Corporation MCR-302

[0088] [1] Modulation of thermosetting components [Comparative Example 1] Add the following to a 600mL mixing container for a rotary mixer: 54.4g of vinyl-containing MQ resin (manufactured by Wacker Chemie) as polysiloxane (a1), 7.3g of p-menthane (manufactured by Nippon Terpene Chemicals Co., Ltd.) as solvent, 3.1g of propylene glycol 1-monomethyl ether 2-acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a second solvent, and 0.22g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a crosslinking inhibitor. Stir the mixture for 5 minutes using a rotary mixer to obtain mixture (I). To the obtained mixture (I), add 8.3 g of SiH-based linear polydimethylsiloxane (manufactured by Wacker Chemie AG) with a viscosity of 100 mPa·s as polysiloxane (a2) and 24.5 g of vinyl-based linear polydimethylsiloxane (manufactured by Wacker Chemie AG) with a viscosity of 200 mPa·s as polysiloxane (a1), and further stir with a rotary mixer for 5 minutes to obtain mixture (II). In a 50 mL threaded tube, add 0.44 g of platinum catalyst (manufactured by Wacker Chemie AG) as (A2) and 3.6 g of vinyl-based linear polydimethylsiloxane (manufactured by Wacker Chemie AG) with a viscosity of 1000 mPa·s as polysiloxane (a1), and stir with a rotary mixer for 5 minutes to obtain mixture (III). Add 2.0 g of mixture (III) to mixture (II), and further stir for 5 minutes using a rotary mixer. Filter the resulting mixture through a 300-mesh nylon filter to obtain the thermosetting composition. The viscosity of the thermosetting composition, measured by a rotational viscometer, is 700 mPa·s.

[0089] [Example 1] Except for replacing 0.22 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) in Comparative Example 1 with 0.22 g of 4,4'-dimethyl-2,2'-bipyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), the same procedure as in Comparative Example 1 was performed to obtain a thermosetting composition.

[0090] [Example 2] Except for replacing 0.22 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) in Comparative Example 1 with 0.22 g of 5,5'-dimethyl-2,2'-bipyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), the same procedure as in Comparative Example 1 was performed to obtain a thermosetting composition.

[0091] [Example 3] Except that 0.22 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) in Comparative Example 1 was replaced with 0.22 g of 4,4'-di-tert-butyl-2,2'-bipyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), the same procedure as in Comparative Example 1 was performed to obtain a thermosetting composition.

[0092] [Example 4] Except for replacing 0.22 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) in Comparative Example 1 with 0.22 g of 4,4'-dinonyl-2,2'-bipyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), the same procedure as in Comparative Example 1 was performed to obtain a thermosetting composition. Furthermore, the nonyl group of 4,4'-dinonyl-2,2'-bipyridine is a normal nonyl group.

[0093] [Example 5] Except for replacing 0.22 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) in Comparative Example 1 with 0.22 g of 4,5-diazamine-9-one (manufactured by Tokyo Chemical Industry Co., Ltd.), the same procedure as in Comparative Example 1 was performed to obtain a thermosetting composition.

[0094] [Example 6] Except for replacing 0.22 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) in Comparative Example 1 with 0.22 g of tributylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd., (CH 3CH 2CH 2CH 2) 3P), the same procedure as in Comparative Example 1 was performed to obtain the thermosetting composition.

[0095] [Example 7] Except for replacing 0.22 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) in Comparative Example 1 with 0.22 g of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), the same procedure as in Comparative Example 1 was performed to obtain a thermosetting composition.

[0096] [Example 8] Except for replacing 0.22 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) in Comparative Example 1 with 0.22 g of tris(4-methoxyphenyl)phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), the same procedure as in Comparative Example 1 was performed to obtain a thermosetting composition.

[0097] [Determination of hardening start temperature using a rheometer] The complex viscosity of Comparative Example 1 and the thermosetting compositions obtained in Examples 1 to 8 was measured in a rheometer while heating from 25°C to 200°C at a heating rate of 10°C / min. Based on the measurement results, the temperature at which a viscosity increase of 10 Pa·s or more occurs when the temperature rises by 1°C is defined as the curing onset temperature. The measured temperatures were read in 1°C increments. The results of the curing onset temperature measurements are shown in Table 1.

[0098] [Table 1]

[0099] As shown in Table 1, compared to the crosslinking inhibitor used in Comparative Example 1, the crosslinking inhibitors used in Examples 1 to 8 had a stronger inhibitory effect on the crosslinking reaction, resulting in an increase in the curing start temperature. Since the curing start temperatures differed among Examples 1 to 8, the curing temperature of the composition could be controlled by appropriately selecting the type of inhibitor.

Claims

1. A thermosetting composition comprising a polyorganosiloxane having an alkenyl group having 2 to 40 carbon atoms bonded to silicon atoms, a polyorganosiloxane having a Si-H group, a platinum group metal catalyst, and a crosslinking inhibitor; wherein the crosslinking inhibitor comprises at least one of a compound represented by formula (1-1), a compound represented by formula (1-2), a compound represented by formula (1-3), a compound represented by formula (1-4), and a compound represented by formula (2); wherein the content of the compound represented by formula (2) is 0.1 to 0.5% by mass relative to the nonvolatile components; [Chemical 1] (In formula (1-1), R1 to R6 each independently represent a hydrogen atom or an alkyl group that may have substituents; however, the compound represented by formula (1-1) has at least one alkyl group that may have substituents); In formula (1-2), R1 to R4 each independently represent a hydrogen atom or an alkyl group that may have substituents; R21 and R22 each independently represent an alkyl group that may have substituents; m and n each independently represent an integer from 0 to 4; when m is 2 or more, the multiple R21s are the same or different; when n is 2 or more, the multiple R22s are the same or different; however, the compound represented by formula (1-2) has at least one alkyl group that may have substituents; In formula (1-3), R3 to R6 each independently represent a hydrogen atom or an alkyl group that may have substituents; In formula (1-4), R3 to R6 each independently represent a hydrogen atom or an alkyl group that may have substituents; R23 represents an alkyl group that may have substituents; n represents an integer from 0 to 2; when n is 2, the multiple R23s are the same or different; however, the compound represented by formula (1-4) has at least one alkyl group that may have substituents. [Chemical 2] (In formula (2), R11 to R13 each represent a hydrocarbon group that can have substituents.) 2. The thermosetting composition as described in claim 1, wherein, The crosslinking inhibitor contains a compound represented by formula (1-1), a compound represented by formula (1-2), a compound represented by formula (1-3), or a compound represented by formula (1-4).

3. The thermosetting composition as described in claim 1 or 2, wherein, In formulas (1-1), (1-2), (1-3), and (1-4), R1 and R2 represent hydrogen atoms; R3 to R6 satisfy either (I) or (II) below: (I): R3 and R5 each independently represent alkyl groups; R4 and R6 represent hydrogen atoms; (II): R3 and R5 represent hydrogen atoms; R4 and R6 each independently represent alkyl groups.

4. The thermosetting composition as described in claim 1, wherein, In formulas (1-1), (1-2), (1-3), and (1-4), the carbon number of the alkyl group is 1 to 12, respectively.

5. The thermosetting composition as described in claim 1, wherein, The crosslinking inhibitor contains a compound represented by formula (2).

6. The thermosetting composition as described in claim 1 or 5, wherein, In formula (2), R11 to R13 represent alkyl groups that may have substituents, or phenyl groups that may have substituents, respectively.

7. The thermosetting composition as described in claim 6, wherein, In formula (2), the carbon number of the alkyl group is 1 to 12, respectively.