阅读说明：本技术 倍半硅氧烷衍生物组合物及其用途 (Silsesquioxane derivative composition and use thereof ) 是由 岩濑贤明 藤田武士 于 2019-09-30 设计创作，主要内容包括：为了提高倍半硅氧烷衍生物的耐热性,本发明提供一种倍半硅氧烷衍生物组合物,其含有倍半硅氧烷衍生物和层状化合物。(The present invention provides a silsesquioxane derivative composition containing a silsesquioxane derivative and a layered compound, in order to improve the heat resistance of the silsesquioxane derivative.)

1. A silsesquioxane derivative composition contains a silsesquioxane derivative and a layered compound.

2. The composition according to claim 1, wherein the layered compound is 1 or 2 or more selected from talc and boron nitride.

3. The composition of claim 1 or 2, wherein the layered compound is talc.

4. A composition according to any one of claims 1 to 3, wherein the lamellar compound has an average particle size of 5 μm or less.

5. The composition according to any one of claims 1 to 4, wherein the layered compound material is contained in an amount of 5 mass% or more and 50 mass% or less relative to the total mass of the silsesquioxane derivative and the layered compound.

6. The composition of any one of claims 1 to 5, wherein the composition further comprises an oxygen storage material.

7. A silsesquioxane derivative composition contains a silsesquioxane derivative and an oxygen storage material.

8. The composition according to claim 6 or 7, wherein the oxygen storage material is 1 or 2 or more selected from ceria, zirconia, and a ceria-zirconia composite oxide.

9. The composition according to any one of claims 6 to 8, wherein the oxygen storage material is a ceria-zirconia composite oxide.

10. The composition according to any one of claims 6 to 9, wherein the oxygen storage material is contained in an amount of 0.1 mass% or more and 40 mass% or less relative to the total mass of the silsesquioxane derivative and the oxygen storage material.

11. The composition of any one of claims 1 to 10, wherein the silsesquioxane derivative has a polymerizable functional group.

12. A curable silsesquioxane derivative composition having: silsesquioxane derivatives having a polymerizable functional group, and layered compounds and/or oxygen storage materials.

13. A silsesquioxane derivative cured product composition comprising: a cured product of a silsesquioxane derivative having a polymerizable functional group, and a layered compound and/or an oxygen storage material.

14. A method for inhibiting oxidation of a silsesquioxane derivative or a cured product thereof, comprising: and heating the silsesquioxane derivative together with the layered compound and/or the oxygen storage material.

15. A method for improving the heat resistance of a silsesquioxane derivative or a cured product thereof, comprising: and heating the silsesquioxane derivative together with the layered compound and/or the oxygen storage material.

16. An oxidation inhibitor for silsesquioxane derivatives or cured products thereof, which comprises a layered compound and/or an oxygen storage material as an active ingredient.

17. A heat resistance improver for a silsesquioxane derivative or a cured product thereof contains a layered compound and/or an oxygen storage material as an active ingredient.

Technical Field

The present invention relates to compositions containing silsesquioxane derivatives and uses thereof.

(cross-reference to related applications)

The present application is related to japanese patent application No. 2018-196951 filed on 10/18/2018, and it is claimed to incorporate the entire contents described in the japanese application based on the priority of the japanese application.

Background

The silsesquioxane is of RSiO_1.5The unit shown as a structural unit of the compound having a three-dimensional crosslinked structure based on a siloxane bond may have, as R, various functional groups represented by organic functional groups. The derivative of silsesquioxane (silsesquioxane derivative) is known as an excellent heat-resistant material (patent documents 1 and 2). Further, the silsesquioxane derivative is an inorganic-organic hybrid material, and therefore can exhibit organic characteristics such as flexibility and solubility in addition to inorganic characteristics such as heat resistance. For example, some silsesquioxane derivatives have a polymerizable functional group such as an epoxy group as an organic group, and thus are used as a curable adhesive and the like (patent document 3).

Documents of the prior art

Patent document

Patent document 1: international publication No. 2005/10077

Patent document 2: international publication No. 2009/66608

Patent document 3: japanese patent laid-open publication No. 2018-95819

Disclosure of Invention

The present inventors have found that the organic group of the silsesquioxane derivative is oxidized depending on conditions such as an atmosphere and a heating temperature, and thus the original characteristics of the silsesquioxane may be changed, for example, mechanical characteristics at high temperature are reduced.

However, no technique for suppressing oxidation of organic groups in silsesquioxane has been reported. Further, silsesquioxane is known to have high heat resistance, and therefore an effective technique for further improving its heat resistance is not provided. Further, no study has been made to ensure heat resistance under severe conditions such that organic groups in silsesquioxane are oxidized.

The present invention provides a technique for enhancing heat resistance by inhibiting oxidation of silsesquioxane and use thereof.

The present inventors have focused on the possibility of an additive capable of inhibiting oxidation of an organic group in a silsesquioxane derivative, and have searched for such an additive. As a result, it was found that both the layered compound and the oxygen storage material can suppress oxidation of the silsesquioxane derivative, and as a result, the heat resistance of the silsesquioxane derivative can be improved. The present specification provides the following means based on these findings.

[1] A silsesquioxane derivative composition contains a silsesquioxane derivative and a layered compound.

[2] The composition according to [1], wherein the layered compound is 1 or 2 or more selected from talc and boron nitride.

[3] The composition according to [1] or [2], wherein the layered compound is talc.

[4] The composition according to any one of [1] to [3], wherein the layered compound has an average particle diameter of 5 μm or less.

[5] The composition according to any one of [1] to [4], wherein the layered compound material is contained in an amount of 5 mass% or more and 50 mass% or less with respect to the total mass of the silsesquioxane derivative and the layered compound.

[6] The composition according to any one of [1] to [5], wherein the composition further contains an oxygen storage material.

[7] A silsesquioxane derivative composition contains a silsesquioxane derivative and an oxygen storage material.

[8] The composition according to [6] or [7], wherein the oxygen storage material is 1 or 2 or more selected from ceria, zirconia, and a ceria-zirconia composite oxide.

[9] The composition according to any one of [6] to [8], wherein the oxygen storage material is a ceria-zirconia composite oxide.

[10] The composition according to any one of [6] to [9], wherein the oxygen storage material is contained in an amount of 0.1 mass% or more and 40 mass% or less with respect to the total mass of the silsesquioxane derivative and the oxygen storage material.

[11] The composition according to any one of [1] to [10], wherein the silsesquioxane derivative has a polymerizable functional group.

[12] A curable silsesquioxane derivative composition having: silsesquioxane derivatives having a polymerizable functional group, and layered compounds and/or oxygen storage materials.

[13] A silsesquioxane derivative cured product composition comprising: a cured product of a silsesquioxane derivative having a polymerizable functional group, and a layered compound and/or an oxygen storage material.

[14] A method for inhibiting oxidation of a silsesquioxane derivative or a cured product thereof, comprising: and heating the silsesquioxane derivative together with the layered compound and/or the oxygen storage material.

[15] A method for improving the heat resistance of a silsesquioxane derivative or a cured product thereof, comprising: and heating the silsesquioxane derivative together with the layered compound and/or the oxygen storage material.

[16] An oxidation inhibitor for silsesquioxane derivatives or cured products thereof, which comprises a layered compound and/or an oxygen storage material as an active ingredient.

[17] A heat resistance improver for a silsesquioxane derivative or a cured product thereof contains a layered compound and/or an oxygen storage material as an active ingredient.

Drawings

Fig. 1 is a graph showing the thermal behavior of silsesquioxane derivatives having a methacryloyl group.

Fig. 2 is a graph showing the thermal behavior of a cured product of the silsesquioxane derivative.

Fig. 3 is a graph showing the thermal behavior of other silsesquioxane derivatives having an oxetanyl group and an epoxy group.

Detailed Description

The present disclosure relates to a technique for further improving the heat resistance of a silsesquioxane derivative by imparting oxidation resistance to the silsesquioxane derivative. According to the disclosure of the present invention, the presence of the layered compound can suppress oxidation of the silsesquioxane derivative, and can improve the stability, particularly the thermal stability (heat resistance), of the silsesquioxane derivative. The reason why the above-mentioned effect is exerted by the layered compound is not clear. The gas barrier property and the gas diffusion suppressing property of the layered compound are considered to be related to the oxidation suppression of the organic group.

Further, the present invention discloses that the presence of an oxygen storage material can inhibit oxidation of the silsesquioxane derivative, and can improve the stability, particularly the thermal stability (heat resistance), of the silsesquioxane derivative. It is considered that the effect is caused by self-oxidation/reduction due to the oxygen storage material, adsorption of oxygen, or the like.

The silsesquioxane derivative may have various organic groups, and for example, may have a polymerizable functional group. When the silsesquioxane derivative is polymerized, decomposition or the like due to oxidation of the polymerizable functional group may significantly affect the characteristics of the silsesquioxane derivative. Therefore, it is significant to impart oxidation resistance to a silsesquioxane derivative composition containing a silsesquioxane derivative having the functional group and a cured product obtained from the composition by using a layered compound and/or an oxygen storage material.

Hereinafter, representative, non-limiting examples of the present invention will be described in detail with reference to the accompanying drawings. This detailed description is intended only to show those skilled in the art details of preferred examples for implementing the invention, and is not intended to limit the scope of the invention. In addition, in order to provide a further improved "silsesquioxane derivative composition and use thereof", additional features and inventions disclosed below may be used separately or together with other features, inventions.

In addition, combinations of features and steps disclosed in the following detailed description are not essential to the implementation of the present invention in the broadest sense, and are described in order to describe representative specific examples of the present invention. Furthermore, the various features of the representative examples above and below, as well as the various features recited in the independent and dependent claims, do not necessarily have to be combined in the order recited or in the specific examples described herein in order to provide additional and useful embodiments of the present invention.

In addition to the features described in the examples and/or claims, all of the features described in the present specification and/or claims are intended to be disclosed separately and independently of each other as limitations on the specific matters disclosed and claimed at the outset. Further, all the numerical ranges and groups or groups described are intended to disclose intermediate configurations thereof as limitations to the specific matters disclosed and claimed at the beginning of the application.

Various embodiments of the oxidation inhibition technique of the silsesquioxane derivative according to the present invention and the use thereof will be described below. Specifically, a silsesquioxane derivative composition, a silsesquioxane derivative cured product composition, a method for suppressing oxidation or improving heat resistance of silsesquioxane, an oxidation inhibitor of silsesquioxane, a heat resistance improver, and the like will be described.

(silsesquioxane derivative composition)

The silsesquioxane derivative composition disclosed in the present specification (hereinafter also simply referred to as the present composition) contains a silsesquioxane derivative, and a layered compound and/or an oxygen storage material.

(silsesquioxane derivative)

In the present specification, the silsesquioxane means that the main chain skeleton is composed of Si-O bonds and contains (RSiO)_1.5) A polysiloxane of units. The silsesquioxane derivative in the present specification is a mixture of 1 or 2 or more of the polysiloxane and (RSiO)_1.5) (T unit) is a compound of the unit represented by the formula (I).

The silsesquioxane derivative can be represented by the following formula (1) having the structural units (1-1), (1-2), (1-3), (1-4), and (1-5), for example. V, w, x, y and z in formula (1) represent the number of moles of the structural units (1-1) to (1-5), respectively. In formula (1), v, w, x, y and z are average values of the ratio of the number of moles of each structural unit contained in 1 molecule of the silsesquioxane derivative.

The structural units (1-2) to (1-5) in the formula (1) may be 1 type or 2 or more types, respectively. The condensation form of the structural units of the actual silsesquioxane derivative is not limited to the order of arrangement shown in formula (1), and is not particularly limited.

[ chemical formula 1]

[ chemical formula 2]

The silsesquioxane derivative may be provided in combination with at least one polymerizable functional group in a structural unit selected from the group consisting of 5 structural units in formula (1), i.e., structural unit (1-1), structural unit (1-2), structural unit (1-3), and structural unit (1-4).

Further, the silsesquioxane derivative contains at least the structural unit (1-2). The silsesquioxane derivative may further include the structural unit (1-3) together with the structural unit (1-2). For example, in the formula (1), w is a positive number. For example, in the formula (1), w and x are positive numbers, and v, y and z are 0 or positive numbers. The silsesquioxane derivative may be composed of only the structural units (1-2) (w is positive, and the others are 0).

< structural unit (1-1): q Unit >

The structural unit is represented by the formula (1), and a Q unit is defined as a basic structural unit of polysiloxane. The number of the structural units in the silsesquioxane derivative is not particularly limited.

< structural unit (1-2): t Unit >

The structural unit specifies a T unit as a basic structural unit of the polysiloxane. R of the structural unit¹Can be selected from hydrogen atoms and alkyl groups having 1 to 10 carbon atoms (hereinafter also simply referred to as units, C)_1-10Alkyl), alkenyl with 1-10 carbon atoms, alkynyl with 1-10 carbon atoms, aryl, aralkyl and polymerizable functional group.

R¹May be a hydrogen atom. In the case of a hydrogen atom, for example, in the case where the present structural unit and/or the other structural unit has an organic group having 2 to 10 carbon atoms containing a carbon-carbon unsaturated bond capable of undergoing a hydrosilylation reaction (hereinafter, also simply referred to as an unsaturated organic group) included in the polymerizable functional group, a crosslinking reaction can be performed between these units.

R¹Can be C_1-10An alkyl group. C_1-10The alkyl group may be either an aliphatic group or an alicyclic group, or may be either a straight chain or a branched chain. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. The alkyl group is a linear alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc., and is a linear alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, etc. Further examples thereof are methyl groups.

R¹Can be C_1-10An alkenyl group. C_1-10The alkenyl group may be any of an aliphatic group, an alicyclic group, and an aromatic group, and may be either linear or branched. Specific examples of the alkenyl group include a vinyl group (vinyl group), an o-styryl group, an m-styryl group, a p-styryl group, a 1-propenyl group, a 2-propenyl group (allyl group), a 1-butenyl group, a 1-pentenyl group, a 3-methyl-1-butenyl group, a phenylvinyl group, an allyl group (2-propenyl group), and an octenyl group (7-octen-1-yl group).

R¹Can be C_1-10Alkynyl. C_1-10The alkynyl group may be any of an aliphatic group, an alicyclic group and an aromatic group, and may be either linear or branched. Specific examples of the alkynyl group include ethynyl, 1-propynyl, 1-butynyl, 1-pentynyl, 3-methyl-1-butynyl, phenylbutynyl and the like.

R¹May be an aryl group. The number of carbon atoms is, for example, 6 or more and 20 or less, and the number of carbon atoms is, for example, 6 or more and 10 or less. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

R¹May be an aralkyl group. The number of carbon atoms is, for example, 7 or more and 20 or less, and the number of carbon atoms is, for example, 7 or more and 10 or less. Examples of the aralkyl group include phenylalkyl groups such as a benzyl group.

R¹May be a polymerizable functional group. Examples of the polymerizable functional group include polymerizable functional groups that can be cured by heat or light. The polymerizable functional group is not particularly limited, and includes the already-described functional groups such as a vinyl group, an allyl group, and a styryl group, and examples thereof include functional groups having a methacryloyl group, an acryloyl group, an acryloyloxy group, a methacryloyloxy group, an α -methylstyrene group, a vinyl ether group, a vinyl ester group, an acrylamide group, a methacrylamide group, an N-vinylamide group, a maleate group, a fumarate group, an N-substituted maleimide group, an isocyanate group, an oxetanyl group, and an epoxy group. Among them, polymerizable functional groups having a (meth) acryloyl group, an oxetanyl group and an epoxy group are exemplified.

The polymerizable functional group having a (meth) acryloyl group is preferably, for example, a group represented by the following formula or a group containing such a group.

[ chemical formula 3]

In the above formula, R⁵Represents a hydrogen atom or a methyl group, R⁶Represents an alkylene group having 1 to 10 carbon atoms. As R⁶Preferably, the alkylene group has 2 to 10 carbon atoms.

The oxetanyl group is not particularly limited, and examples thereof include (3-ethyl-3-oxetanyl) methoxy group, (3-ethyl-3-oxetanyl) oxy group and the like. The oxetanyl group-containing group is preferably a group represented by the following formula or a group containing the group.

[ chemical formula 4]

In the above formula, R⁷Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R⁸Represents an alkylene group having 1 to 6 carbon atoms. As R⁷The hydrogen atom, methyl group and ethyl group are preferable, and the ethyl group is more preferable. As R⁸Preferably, the alkylene group has 2 to 6 carbon atoms, and more preferably the propenyl group.

Examples of the epoxy group include, but are not particularly limited to, alkyl groups having 1 to 10 carbon atoms, such as a β -glycidoxyethyl group, a γ -glycidoxypropyl group, and a γ -glycidoxybutyl group, which are substituted with a glycidoxy group, glycidyl groups, β - (3, 4-epoxycyclohexyl) ethyl groups, γ - (3, 4-epoxycyclohexyl) propyl groups, β - (3, 4-epoxycycloheptyl) ethyl groups, 4- (3, 4-epoxycyclohexyl) butyl groups, and 5- (3, 4-epoxycyclohexyl) pentyl groups, which are substituted with a cycloalkyl group having 5 to 8 carbon atoms and an oxirane group.

The polymerizable functional group may be an unsaturated organic group as described above, that is, a functional group having a carbon-carbon double bond or a carbon-carbon triple bond capable of undergoing a hydrosilylation reaction with a hydrogen atom (hydrosilyl group) bonded to a silicon atom. Since a hydrogen atom is present in the hydrosilyl group, the unsaturated organic group can also function as a polymerizable functional group in the meaning that the unsaturated organic group is polymerized with the hydrogen atom by a hydrosilylation reaction to form a hydrosilylation structural portion. Specific examples of the unsaturated organic group include the alkenyl group and the alkynyl group. Examples of the substituent include, but are not particularly limited to, vinyl, o-styryl, m-styryl, p-styryl, acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, 1-propenyl, 1-butenyl, 1-pentenyl, 3-methyl-1-butenyl, phenylvinyl, ethynyl, 1-propynyl, 1-butynyl, 1-pentynyl, 3-methyl-1-butynyl, phenylbutynyl, allyl (2-propenyl), and octenyl (7-octen-1-yl). The unsaturated organic group is, for example, vinyl, p-styryl, allyl (2-propenyl), octenyl (7-octen-1-yl), and further, for example, vinyl.

The silsesquioxane derivative may contain 2 or more polymerizable functional groups in its entirety, and in this case, all the polymerizable functional groups may be the same as or different from each other. The plurality of polymerizable functional groups may be the same or may further include different polymerizable functional groups.

C_1-10Alkyl radical, C_1-10Alkenyl radical, C_1-10The alkynyl, aryl, aralkyl, and polymerizable functional groups may be substituted. The substituent may be substituted with at least 1 or more of a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or a chlorine atom, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, or an isooctyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an oxy group (═ O), a cyano group.

The protecting group of the protected hydroxyl group is not particularly limited, and a known protecting group of a hydroxyl group can be used. Examples of the protective group include an acyl-based protective group represented by — C (═ O) R (wherein R represents an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group, or a substituted or unsubstituted phenyl group, and the substituted phenyl group has an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and an isooctyl group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, an alkoxy group such as a methoxy group and an ethoxy group, a trimethylsilyl group, a triethylsilyl group, a; acetal-based protecting groups such as methoxymethyl, methoxyethoxymethyl, 1-ethoxyethyl, tetrahydropyran-2-yl and tetrahydrofuran-2-yl; alkoxycarbonyl-based protecting groups such as tert-butoxycarbonyl; and ether-based protecting groups such as methyl, ethyl, tert-butyl, octyl, allyl, triphenylmethyl, benzyl, p-methoxybenzyl, fluorenyl, trityl, and benzhydryl.

The silsesquioxane derivative may be combined with 1 or 2 or more species having the present structural unit. For example, R of 1 structural unit may be¹R as alkyl to 1 other structural unit¹A polymerizable functional group. Furthermore, for example, R of 1 structural unit may be¹R as hydrogen atom, another 1 structural unit¹An unsaturated organic group as a polymerizable functional group is used.

The ratio w of the number of moles of the present structural unit in the silsesquioxane derivative is a positive number. w is not particularly limited, and is, for example, 0.25 or more, further 0.3 or more, further 0.35 or more, further 0.4 or more, further 0.5 or more, further 0.6 or more, further 0.7 or more, further 0.8 or more, further 0.9 or more, further 0.95 or more, further 0.99 or more, and further 1 or 1, for example.

< structural unit (1-3): d Unit >

The present structural unit specifies a D unit as a basic structural unit of the silsesquioxane derivative. R of the structural unit²Can be selected from hydrogen atoms, C_1-10Alkyl radical, C_1-10Alkenyl radical, C_1-10Alkynyl, aryl, aralkyl, polymerizable functional group. R in the structural unit²May be the same or different.

For C_1-10Alkyl radical, C_1-10Alkenyl radical, C_1-10The alkynyl group, the aryl group, the aralkyl group, and the polymerizable functional group can be applied to the structural unit in various forms as described above.

The silsesquioxane derivative may have 1 or 2 or more of the structural units in combination. In silsesquioxane derivatives, for example, 2R for at least a part of the structural units²Are all C_1-10Alkyl radicals, and also, for example, 2R for all of the structural units²Are all C_1-10An alkyl group.

The ratio x of the number of moles of the present structural unit in the silsesquioxane derivative is 0 or a positive number. x is not particularly limited, and is, for example, 0.25 or more, 0.3 or more, 0.35 or more, and 0.4 or more, for example. This numerical value is, for example, 0.5 or less, and is, for example, 0.45 or less.

< structural unit (1-4): m Unit >

The present structural unit specifies an M unit as a basic structural unit of the silsesquioxane derivative. R of the structural unit³Can be selected from hydrogen atoms, C_1-10Alkyl radical, C_1-10Alkenyl radical, C_1-10Alkynyl, aryl, aralkyl, polymerizable functional group. Can be selected from a hydrogen atom, a polymerizable functional group, and C_1-10At least 1 of the alkyl groups. R in the structural unit³May be the same or different.

For C_1-10Alkyl radical, C_1-10Alkenyl radical, C_1-10The alkynyl group, the aryl group, the aralkyl group, and the polymerizable functional group can be applied to the structural unit in various forms as described above.

The silsesquioxane derivative may have 1 or 2 or more of the structural units in combination. In silsesquioxane derivatives, for example, 2R for at least a part of the structural units³Are all C_1-10Alkyl radicals, and also, for example, 2R for all of the structural units³Are all C_1-10An alkyl group.

The ratio y of the number of moles of the present structural unit in the silsesquioxane derivative is 0 or a positive number. y is not particularly limited, and is, for example, 0.25 or more, 0.3 or more, 0.35 or more, and 0.4 or more, for example. This numerical value is, for example, 0.5 or less, and is, for example, 0.45 or less.

< structural Unit (1-5) >)

The present structural unit specifies a unit containing an alkoxy group or a hydroxyl group in the silsesquioxane derivative. Namely, R in the present structural unit⁴Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group may be either an aliphatic group or an alicyclic group, or may be either a straight chain or a branched chain. As a specific example of the alkyl group, there may be mentionedExamples thereof include methyl, ethyl, n-propyl, isopropyl, butyl, pentyl and hexyl. Typically, the alkyl group has 2 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, and the like, and the alkyl group has 1 to 6 carbon atoms.

The alkoxy group in the present structural unit is an "alkoxy group" which is a hydrolyzable group contained in a raw material monomer described later, or an "alkoxy group" which is generated by substituting an alcohol contained in a reaction solvent with a hydrolyzable group of a raw material monomer, and remains in the molecule without hydrolysis and polycondensation. The hydroxyl group in the structural unit is a hydroxyl group or the like which remains in the molecule without polycondensation after hydrolysis of the "alkoxy group".

The ratio z of the number of moles of the present structural unit in the silsesquioxane derivative is 0 or a positive number.

The silsesquioxane derivative preferably has 1 or 2 or more kinds selected from the structural unit (1-1), the structural unit (1-3), and the structural unit (1-4). That is, in the formula (1), 1 or 2 or more of v, x and y are preferably positive numbers.

< molecular weight et al >

The number average molecular weight of the silsesquioxane derivative is preferably in the range of 300 to 10,000. The silsesquioxane derivative is low in viscosity, is easily dissolved in an organic solvent, is easy to handle due to the viscosity of the solution, and has excellent storage stability. The number average molecular weight is preferably 300 to 8,000, more preferably 300 to 6,000, more preferably 300 to 3,000, more preferably 300 to 2,000, more preferably 500 to 2,000, in view of coatability, storage stability, heat resistance and the like. The number average molecular weight can be determined by GPC (gel permeation chromatograph) using polystyrene as a standard substance under the measurement conditions described below in [ example ].

The silsesquioxane derivative is preferably in a liquid state. When the silsesquioxane derivative is a liquid, the viscosity at 25 ℃ is, for example, 500mPa · s or more, more preferably 1000mPa · s or more, and still more preferably 2000mPa · s or more, from the viewpoint of mixing the filler.

< method for producing silsesquioxane derivative >

The silsesquioxane derivative can be produced by a known method. The method for producing silsesquioxane derivatives is disclosed in detail in, for example, WO 2005/010077, WO 2009/066608, WO 2013/099909, Japanese patent laid-open Nos. 2011-052170 and 2013-147659 as a method for producing polysiloxanes.

The silsesquioxane derivative can be produced, for example, by the following method. That is, the method for producing a silsesquioxane derivative may have: a condensation step in which a hydrolysis/polycondensation reaction of the raw material monomer providing the structural unit of formula (1) is carried out by condensation in an appropriate reaction solvent. In this condensation step, a silicon compound having 4 siloxane bond-generating groups (hereinafter referred to as "Q monomer") that forms the structural unit (1-1), a silicon compound having 3 siloxane bond-generating groups (hereinafter referred to as "T monomer") that forms the structural unit (1-2), a silicon compound having 2 siloxane bond-generating groups (hereinafter referred to as "D monomer") that forms the structural unit (1-3), and a silicon compound having 1 siloxane bond-generating group (1-4) (hereinafter referred to as "M monomer") can be used.

In the present specification, specifically, among a Q monomer forming the structural unit (1-1), a T monomer forming the structural unit (1-2), a D monomer forming the structural unit (1-3), and an M monomer forming the structural unit (1-4), at least the T monomer is used. It is preferable to have a distillation step of subjecting the raw material monomer to hydrolysis and polycondensation reaction in the presence of the reaction solvent, and thereafter distilling off the reaction solvent, the side reaction product, the residual monomer, water, and the like in the reaction liquid.

The siloxane bond-generating group contained in the Q monomer, T monomer, D monomer or M monomer as the raw material monomer is a hydroxyl group or a hydrolyzable group. Among them, examples of the hydrolyzable group include a halogeno group, an alkoxy group, and the like. At least 1 of the Q monomer, T monomer, D monomer and M monomer preferably has a hydrolyzable group. In the condensation step, since the hydrolyzability is good and no acid is produced as a by-product, the hydrolyzable group is preferably an alkoxy group, and more preferably an alkoxy group having 1 to 4 carbon atoms.

In the synthesis of the silsesquioxane derivative, an organosilicon compound having a siloxane bond-generating group represented by the following formulae (2) and (3) (hereinafter also referred to as a D oligomer) may be used instead of the D monomer.

[ chemical formula 5]

(in the above formulae (2) and (3), X is a siloxane bond-forming group, R⁹And R¹²Each is alkoxy, aryloxy, alkyl, cycloalkyl or aryl, R¹⁰、R¹¹And R¹³Each is an alkyl, cycloalkyl or aryl group, and m and n are positive integers).

The siloxane bond-forming group of the D oligomer is an atom or an atomic group capable of forming a siloxane bond with a silicon atom in the silane compound, and specific examples thereof include an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, or a tert-butoxy group, a cycloalkoxy group such as a cyclohexyloxy group, an aryloxy group such as a phenoxy group, a hydroxyl group, a hydrogen atom, and the like. The D oligomer represented by formula 2 has 2 siloxane bond-generating groups in one molecule, and they may be the same group or different groups.

As the D oligomer, an oligomer in which a siloxane bond-generating group is a hydroxyl group is easily available.

R of D oligomer⁹And R¹²Each is an alkoxy group, an aryloxy group, an alkyl group, a cycloalkyl group or an aryl group, and 2R's are present in one molecule⁹And R¹²Each may be the same group or different groups. R⁹And R¹²Specific examples thereof include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, cyclohexyloxy group, phenoxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, phenyl group and the like.

R of D oligomer¹⁰、R¹¹And R¹³Each is an alkyl group,Cycloalkyl or aryl, R being present in more than one molecule¹⁰And R¹¹Each may be the same group or different groups. R¹⁰、R¹¹And R¹³Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl and phenyl groups. The D oligomer is preferably a compound having a plurality of R groups in one molecule, because it can be produced from inexpensive raw materials and a cured product obtained using the present composition is excellent in, for example, adhesiveness and the like¹⁰And R¹¹Oligomers which are methyl or phenyl groups, especially more preferably all methyl groups.

In the D oligomer, the number m and n of the repeating units are positive integers, and the D oligomer is preferably one in which m and n are 10 to 100, and more preferably 10 to 50.

In the condensation step, it is preferable that the siloxane bond-generating group of the Q monomer, the T monomer, or the D monomer or the D oligomer corresponding to each structural unit is an alkoxy group, and the siloxane bond-generating group contained in the M monomer is an alkoxy group or a siloxy group. Further, the monomer and oligomer corresponding to each structural unit may be used alone, or 2 or more kinds may be used in combination.

Examples of the Q monomer providing the structural unit (1-1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like. Examples of the T monomer that provides the structural unit (1-2) include trimethoxysilane, triethoxysilane, tripropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, and trichlorosilane. Examples of the T monomer providing the structural unit (1-2) include trimethoxyvinylsilane, triethoxyvinylsilane, vinyltris (2-methoxyethoxy) silane, trimethoxyallylsilane, triethoxyallylsilane, trimethoxy (7-octen-1-yl) silane, (p-styryl) trimethoxysilane, (p-styryl) triethoxysilane, (3-methacryloxypropyl) trimethoxysilane, (3-methacryloxypropyl) triethoxysilane, (3-acryloxypropyl) trimethoxysilane, and (3-acryloxypropyl) triethoxysilane. Examples of the monomer D for providing the structural unit (1-3) include dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, diethoxydiethylsilane, dipropoxydimethylsilane, dipropoxydiethylsilane, dimethoxyphenylmethylsilane, diethoxybenzylmethylsilane, dichlorodimethylsilane, dimethoxymethylsilane, dimethoxymethylvinylsilane, diethoxymethylsilane, and diethoxymethylvinylsilane. Examples of the M monomer which can provide the structural unit (1-4) include hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, 1,3, 3-tetramethyldisiloxane, 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane, methoxydimethylsilane, ethoxydimethylsilane, methoxydimethylvinylsilane, and ethoxydimethylvinylsilane which can provide 2 structural units (1-4) by hydrolysis, and examples thereof include methoxytrimethylsilane, ethoxytrimethylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorodimethylsilane, chlorodimethylvinylsilane, chlorotrimethylsilane, dimethylsilanol, dimethylvinylsiloxane, trimethylsilanol, triethylsilanol, and the like, Tripropylsilanol, tributylsilanol, and the like. Examples of the organic compound that provides the structural unit (1-5) include alcohols such as 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, methanol, and ethanol. Compositions comprising these monomers for obtaining silsesquioxane derivatives are also provided in accordance with the above description.

In the condensation step, an alcohol may be used as a reaction solvent. The alcohol is a narrow alcohol represented by the general formula R-OH, and is a compound having no functional group other than an alcoholic hydroxyl group. Although not particularly limited, examples of the specific examples include methanol, ethanol, n-propanol, isopropanol, 2-butanol, 2-pentanol, 3-pentanol, 2-methyl-2-butanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2-ethyl-2-butanol, 2, 3-dimethyl-2-butanol, and cyclohexanol. Among these, secondary alcohols such as isopropyl alcohol, 2-butanol, 2-pentanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-methyl-2-pentanol, and cyclohexanol can be used. In the condensation step, these alcohols may be used in 1 kind or in combination of 2 or more kinds. More preferably, the alcohol is a compound capable of dissolving water at a required concentration in the condensation step. The alcohol having such properties is a compound having a solubility of 10g or more per 100g of water in the alcohol at 20 ℃.

The alcohol used in the condensation step may further include an additional input part in the middle of the hydrolysis/polycondensation reaction, and the gelation of the silsesquioxane derivative to be produced can be suppressed by using 0.5 mass% or more of the total amount of all reaction solvents. The amount used is preferably 1 mass% or more and 60 mass% or less, and more preferably 3 mass% or more and 40 mass% or less.

The reaction solvent used in the condensation step may be an alcohol alone, or may be a mixed solvent with at least 1 type of side solvent. The secondary solvent may be either one of a polar solvent and a nonpolar solvent, or a combination of both. As the polar solvent, preferred solvents are secondary or tertiary alcohols having 3 or 7 to 10 carbon atoms, diols having 2 to 20 carbon atoms, and the like. When a primary alcohol is used as the secondary solvent, the amount of the secondary solvent used is preferably 5 mass% or less of the entire reaction solvent. The preferred polar solvent is 2-propanol which can be industrially obtained at low cost, and by using 2-propanol and the alcohol of the present invention in combination, even when the alcohol of the present invention cannot dissolve water at a concentration required in the hydrolysis step, a required amount of water can be dissolved together with the polar solvent, and the effects of the present invention can be obtained. The amount of the polar solvent is preferably 20 parts by mass or less, more preferably 1 to 20 parts by mass, and particularly preferably 3 to 10 parts by mass, based on 1 part by mass of the alcohol of the present invention.

The nonpolar solvent is not particularly limited, and examples thereof include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, alcohols, ethers, amides, ketones, esters, cellosolves, and the like. Among these, aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons are preferable. Such a nonpolar solvent is not particularly limited, and for example, n-hexane, isohexane, cyclohexane, heptane, toluene, xylene, dichloromethane, or the like is azeotroped with water, and therefore, if these compounds are used in combination, it is preferable that water and a polymerization catalyst such as an acid dissolved in water can be efficiently distilled off when the reaction solvent is distilled off from the reaction mixture containing the silsesquioxane derivative after the condensation step. The nonpolar solvent is particularly preferably xylene which is an aromatic hydrocarbon because of its relatively high boiling point. The amount of the nonpolar solvent used is 50 parts by mass or less, more preferably 1 to 30 parts by mass, and particularly preferably 5 to 20 parts by mass, based on 1 part by mass of the alcohol of the present invention.

The hydrolysis and polycondensation reaction in the condensation step is carried out in the presence of water. The amount of water for hydrolyzing the hydrolyzable group contained in the raw material monomer is preferably 0.5 to 5 times by mol, and more preferably 1 to 2 times by mol, based on the hydrolyzable group. The hydrolysis and polycondensation reaction of the raw material monomer may be carried out without a catalyst or with a catalyst. The catalyst used in the hydrolysis/polycondensation reaction is an acid or a base. As the catalyst, inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and the like; and organic acids such as formic acid, acetic acid, oxalic acid, and p-toluenesulfonic acid. The amount of the acid catalyst used is preferably 0.01 to 20 mol%, more preferably 0.1 to 10 mol%, based on the total amount of silicon atoms contained in the raw material monomer.

The completion of the hydrolysis/polycondensation reaction in the condensation step can be appropriately detected by the methods described in the above-mentioned various publications and the like. In the condensation step for producing the silsesquioxane derivative, an auxiliary agent may be added to the reaction system. Examples thereof include an antifoaming agent for suppressing foaming of the reaction solution, a scale control agent for preventing scale adhesion on the reaction tank and the stirring shaft, a polymerization inhibitor, and a hydrosilylation inhibitor. The amount of these auxiliaries used is optional, and is preferably about 1 to 10 mass% relative to the silsesquioxane derivative concentration in the reaction mixture.

Stability and usability of the silsesquioxane derivative to be produced can be improved by including a distillation step of distilling off a reaction solvent, a side reaction product, a residual monomer, water and the like contained in a reaction liquid obtained in the condensation step after the condensation step in the production of the silsesquioxane derivative. In particular, by using a solvent azeotropic with water as a reaction solvent and distilling off the solvent at the same time, acids and bases used as a polymerization catalyst can be removed efficiently. Although the distillation depends on the boiling point of the solvent used, reduced pressure conditions may be appropriately used at a temperature of 100 ℃ or lower.

(layered Compound)

The present composition may contain a layered compound. The layered compound is not particularly limited, and 1 or 2 or more kinds of known layered compounds can be used. Examples of the layered compound include a silicate layered compound such as talc (layered magnesium silicate), and minerals such as boron nitride, mica, and montmorillonite. Among them, talc and boron nitride are exemplified.

The layered compound is generally in powder form. The particle shape thereof is not particularly limited. The average particle diameter is not particularly limited, and is preferably 10 μm or less, for example. The reason for this is that if it is 10 μm or less, good oxidation resistance can be obtained. More preferably 5 μm or less. Further, it is more preferably 3 μm or less, and still more preferably 2.5 μm or less. The lower limit is not particularly limited, and is, for example, 0.5 μm or more, or 1.0 μm or more. The average particle size of the layered compound can be measured by a laser diffraction scattering method. In the present specification, the average particle diameter of the layered compound is a particle diameter D50 corresponding to 50 vol% of the cumulative frequency from the side of the fine particles having a small particle diameter in the volume-based particle size distribution by the laser diffraction/scattering method. For the measurement, a dispersion liquid dispersed by ultrasonic waves using a lamellar compound such as talc can be used.

The content of the layered compound in the present composition is not particularly limited, and may be an effective amount for suppressing oxidation of the silsesquioxane derivative to be used. The layered compound may be, for example, 5% by mass or more, further, for example, 10% by mass or more, further, for example, 15% by mass or more, further, for example, 20% by mass or more, further, for example, 25% by mass or more, further, for example, 30% by mass or more, based on the total mass of the silsesquioxane derivative and the layered compound. The amount of the organic solvent may be, for example, 50 mass% or less, 45 mass% or less, 40 mass% or less, or the like. The content of the layered compound may be, for example, 5 mass% or more and 50 mass% or less, 10 mass% or more and 40 mass% or less, or 20 mass% or more and 40 mass% or less, based on the total mass of the silsesquioxane derivative and the layered compound.

(oxygen storage Material)

The present compositions may comprise an oxygen storage material. The oxygen storage material is a material having an oxygen storage capacity. The oxygen storage material is not particularly limited, and known oxygen storage materials can be used, and examples thereof include alumina, titania, zirconia, ceria, and iron oxide (Fe)₂O₃) Ceria-zirconia composite oxide, a specific type of perovskite metal oxide, and the like. The zirconia and ceria-zirconia composite oxide may be stabilized by a known stabilizer. The oxygen storage material may be doped with other metal atoms in such metal oxides. As the oxygen storage material, for example, ceria, zirconia, ceria-zirconia composite oxide can be preferably used. As the oxygen storage material, 1 or a combination of 2 or more of such known oxygen storage materials can be used.

The oxygen storage material is generally in powder form. The shape of the particles in the powder is not particularly limited. The average particle diameter is not particularly limited, and is preferably 5 μm or less, for example. It is considered that if the thickness is 5 μm or less, the surface area of the film exhibits a high oxygen absorbing ability. More preferably 1 μm or less. Further, it is preferably 500nm or less, more preferably 100nm or less, further preferably 50nm or less, further preferably 30nm or less, and further preferably 20nm or less.

In the present specification, the average particle size of the oxygen storage material is obtained by calculating the particle size by determining the specific surface area by the BET method when the average particle size is less than 1 μm. Namely, according to the use of nitrogen gas (N)₂) The specific surface area (m) of the gas adsorption amount measured as the gas adsorption method of the adsorbate was analyzed by the BET method (multipoint method or 1-point method)²(g, S), the average particle diameter can be determined. In the measurement of the amount of nitrogen adsorbed, the sample degassed at 300 ℃ for 12 hours or more under vacuum was subjected to gas adsorption at 77K. When the average particle size is 1 μm or more, the average particle size is calculated by a laser diffraction scattering method described with respect to the average particle size of the layered compound.

The content of the oxygen storage material in the present composition is not particularly limited, and may be an effective amount for suppressing oxidation of the silsesquioxane derivative to be used. The oxygen storage material may be, for example, 0.05% by mass or more, further, for example, 0.1% by mass or more, further, for example, 0.5% by mass or more, further, for example, 1% by mass or more, further, for example, 3% by mass or more, further, for example, 5% by mass or more, further, for example, 10% by mass or more, further, for example, 15% by mass or more, or the like, based on the total mass of the silsesquioxane derivative and the oxygen storage material. The total amount of the inorganic particles may be, for example, 25 mass% or less, or 20 mass% or less. The content of the oxygen storage material may be, for example, 0.05 mass% or more and 50 mass% or less, or, for example, 0.1 mass% or more and 40 mass% or less, based on the total mass of the silsesquioxane derivative and the oxygen storage material.

The present compositions may comprise either or both of a layered compound and an oxygen storage material. When both are contained, the respective intrinsic effects act, and oxidation of the silsesquioxane derivative is effectively suppressed, thereby obtaining excellent heat resistance. When both are contained, each may be contained in the content range described above. When the present composition contains both the layered compound and the oxygen storage material, the total mass of the layered compound and the oxygen storage material may be, for example, 10 mass% or more and 80 mass% or less, 15 mass% or more and 70 mass% or less, or 20 mass% or more and 60 mass% or less, relative to the total mass of the silsesquioxane derivative, the layered compound, and the oxygen storage material.

(embodiment of the present composition)

The present compositions may be used in a variety of ways. The present composition may contain, for example, an uncured silsesquioxane derivative (which is not crosslinked or polymerized by a polymerizable functional group) and is a composition before film formation or molding (typically, an amorphous body such as a liquid body).

The present composition may be a composition such as a film or a molded article formed by forming a cured product of a silsesquioxane derivative on the surface of a workpiece.

(composition containing uncured silsesquioxane derivative)

The present composition of the above embodiment may contain, for example, a silsesquioxane derivative having an organic functional group such as a polymerizable functional group, and a layered compound and/or an oxygen storage material. Further, an initiator and/or a polymerization catalyst (curing agent) required for curing or polymerization may be contained as necessary. The present composition has an uncured silsesquioxane derivative and a layered compound and/or an oxygen storage material, and thus achieves heat resistance of the silsesquioxane derivative or a cured product thereof when the silsesquioxane derivative is exposed to heat, cured by heating, or cured by exposing the cured product to heat. Further, as other components, a solvent may be contained.

(polymerization initiator)

The present composition may include a polymerization initiator for polymerizing the silsesquioxane derivative through a polymerizable functional group. The type of the polymerization initiator differs depending on the type of the polymerizable functional group of the silsesquioxane derivative, and various initiators and curing agents such as a photoinitiator, a thermal initiator, and a radical polymerization initiator can be used. The kind and amount of the polymerization initiator or curing agent can be appropriately selected by those skilled in the art in consideration of the polymerizable functional group to be used and the use of the present composition. For example, as the radical polymerization initiator, a known organic peroxide, azo compound, or the like can be used.

Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide and the like. Further, examples of the azo compound include azobisisobutyronitrile, azobisisovaleronitrile, azobisisobutyronitrile, and the like.

The content of the polymerization initiator is not particularly limited, but is preferably 0.01 to 5% by mass, more preferably 0.5 to 3% by mass, based on the whole composition.

(hydrosilylation catalyst)

When the polymerizable functional group has an unsaturated organic group in the presence of a hydrosilyl hydrogen atom, examples of the hydrosilylation catalyst used for curing (hydrosilylation) by hydrosilylation of the silsesquioxane derivative include simple substances of group VIII such as cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum, organometallic complexes, metal salts, and metal oxides. Typically, a platinum-based catalyst is used. As the platinum-based catalyst, cis-PtCl can be exemplified₂(PhCN)₂Platinum carbon, platinum complex coordinated with 1, 3-divinyltetramethyldisiloxane (Pt (dvs)), platinum vinylmethylcyclosiloxane complex, platinum carbonyl vinylmethylcyclosiloxane complex, tris (diphenylmethyleneacetone) diplatin, chloroplatinic acid, bis (ethylene) tetrachlorodiplatin, cyclooctadienedichloroplatinum, bis (cyclooctadiene) platinum, bis (dimethylphenylphosphine) dichloroplatinum, tetrakis (triphenylphosphine) platinum, and the like. Among these, 1, 3-divinyltetramethyldisiloxane-coordinated platinum complex (pt (dvs)), platinum vinylmethylcyclosiloxane complex, and platinum carbonyl vinylmethylcyclosiloxane complex are particularly preferable. Ph represents a phenyl group. The amount of the catalyst used is preferably 0.1 to 1000 mass ppm, more preferably 0.5 to 100 mass ppm, and still more preferably 1 to 50 mass ppm, relative to the amount of the silsesquioxane derivative.

When the present composition contains a catalyst for hydrosilylation, the hydrosilylation reaction may be more preferred than the dehydration polycondensation of the residual alkoxy groups or hydroxyl groups in the structural units (1 to 5), and the composition may have a hydrosilylation structural moiety and the above-mentioned alkoxy groups or hydroxyl groups capable of further crosslinking reaction.

When the present composition contains a hydrosilylation catalyst, a hydrosilylation reaction inhibitor may be added to suppress gelation of the silsesquioxane derivative and to improve storage stability. Examples of the hydrosilylation reaction inhibitor include methylvinylcyclotetrasiloxane, alkynols, siloxane-modified alkynols, hydroperoxides, hydrosilylation reaction inhibitors containing a nitrogen atom, a sulfur atom, or a phosphorus atom, and the like.

The present composition may be a composition for film formation, or may be a composition substantially free of a hydrosilylation catalyst. As described later, the silsesquioxane derivative can accelerate the hydrosilylation reaction and cure it by heat treatment even in the absence of a hydrosilylation catalyst. The substantial absence of the hydrosilylation catalyst in the present composition means that the content of the hydrosilylation catalyst is, for example, less than 0.1 mass ppm and, for example, 0.05 mass ppm or less relative to the amount of the silsesquioxane derivative, except when the hydrosilylation catalyst is not intentionally added.

(solvent)

The silsesquioxane derivative may be used as it is or diluted with a solvent as necessary to form a film. The solvent is preferably a solvent in which the silsesquioxane derivative is dissolved, and examples thereof include various organic solvents such as an aromatic hydrocarbon solvent, a chlorinated hydrocarbon solvent, an alcohol solvent, an ether solvent, an amide solvent, a ketone solvent, an ester solvent, a cellosolve solvent, and an aliphatic hydrocarbon solvent. In the presence of a hydrosilylation catalyst such as Pt, a solvent other than alcohol is preferred in order to avoid decomposition of Si — H groups.

(other Components)

Various additives may be further added to the present composition when the composition is subjected to curing. Examples of the additive include reactive diluents such as tetraalkoxysilanes and trialkoxysilanes (trialkoxysilanes, trialkoxyvinylsilanes, etc.); monomers and oligomers having a polymerizable functional group which are the same as or similar to the polymerizable functional group of the silsesquioxane derivative. These additives are used in a range that does not impair the heat resistance of the cured product of the obtained silsesquioxane derivative.

By supplying the present composition to the surface of a workpiece having an arbitrary shape and curing the composition to form a film, a film having excellent heat resistance can be formed. For example, the present composition may be supplied to the surface of the site to be processed, and then the composition may be cured.

The composition is not particularly limited to be supplied to the surface of the object to be processed, and a common coating method such as a spray coating method, a casting method, a spin coating method, and a bar coating method can be used.

(composition containing cured product of silsesquioxane derivative)

The composition may also be a composition containing a cured product obtained by polymerizing a silsesquioxane derivative having a polymerizable functional group with the polymerizable functional group. The composition may also contain a layered compound and/or an oxygen storage material. The present composition is obtained by polymerizing a silsesquioxane derivative having such a functional group by heating or the like in the presence of a layered compound and/or an oxygen storage material, for example.

Examples of the cured product of the silsesquioxane derivative include the use of unreacted alkoxy groups in the silsesquioxane derivative, that is, R in the structural unit (1-5)⁴The alkoxy group and the hydroxyl group(s) in (a) form a siloxane bond sufficiently by dehydration and condensation polymerization, and further promote crosslinking, thereby curing (curing by condensation polymerization of the residual alkoxy group and the like is also referred to as primary curing). The cured product (hereinafter also referred to as a primary cured product) may be contained in a silsesquioxane derivative represented by the composition formula (1).

Other cured products of the silsesquioxane derivative include cured products obtained by accelerating crosslinking by reaction of polymerizable functional groups contained in the structural units (1-2) to (1-4) (the curing is also referred to as secondary curing). The cured product (hereinafter also referred to as a secondary cured product) may contain a derivative of a silsesquioxane derivative having a structural moiety obtained by polymerizing at least a part of polymerizable functional groups in these structural units in the silsesquioxane derivative based on polymerizability originally possessed by the functional groups.

Other cured products of the silsesquioxane derivative include cured products obtained by curing (the curing is also referred to as secondary curing) the hydrogen atoms contained in the structural units (1-2) to (1-4) and unsaturated organic groups by hydrosilylation reaction to further promote crosslinking. The cured product (hereinafter also referred to as a secondary cured product) may contain a derivative of a silsesquioxane derivative having a structural moiety derived from a carbon-carbon bond (single bond or double bond) of an unsaturated organic group formed by hydrosilylation of at least part of functional groups (hydrosilyl group and unsaturated organic group) that undergo hydrosilylation in these structural units in the silsesquioxane derivative_m-Si-、-Si-C＝C-R_m-Si) (also referred to as hydrosilylation moiety in the present description; r is an organic group having 1 to 8 carbon atoms, and m is an integer of 0 or 1).

When the present composition is formed into a film, the present composition is a secondary cured product of the silsesquioxane derivative as a whole. In addition to the polymeric moiety utilizing a polymerizable functional group, the hydrosilylation structural moiety can contribute to practical film strength and film performance.

The primary curing of the silsesquioxane derivative is sometimes accompanied by secondary curing, and further, the secondary curing is sometimes accompanied by primary curing, but the secondary curing is accompanied by primary curing in most cases. Therefore, the cured product of the silsesquioxane derivative is a secondary cured product as a whole, and is accompanied by primary curing in most cases. Typical cured products are characterized by the presence or absence of a crosslinked structure by secondary curing. The cured product can be used, for example¹H NMR、²⁹Si NMR analysis of structural units such as Q unit, T unit, D unit, M unit, alkoxy group, etc., and structural regularity(irregularity), and the composition and structure thereof are determined by detecting characteristic groups using IR spectroscopy.

The present composition may contain other components as necessary, in addition to the silsesquioxane derivative or the cured product thereof.

(Oxidation suppressing method and Heat resistance method)

The method for inhibiting oxidation of a silsesquioxane derivative or a cured product thereof disclosed in the present specification may include: and heating the silsesquioxane derivative or a cured product thereof together with the layered compound and/or the oxygen storage material. The oxidation inhibition method is also a method for improving the heat resistance of the silsesquioxane derivative or the cured product thereof. In the various embodiments of the present composition described above, in the step of producing a cured product of the silsesquioxane derivative and the step of heating the cured product, the oxidation of the silsesquioxane derivative or the cured product thereof is suppressed by the layered compound and/or the oxygen storage material. Therefore, by having the above-mentioned step, oxidation of the silsesquioxane derivative or a cured product thereof is suppressed, and heat resistance is achieved.

Thus, according to the present specification, there are provided an oxidation inhibitor or a heat resistance improver for a silsesquioxane derivative or a cured product thereof, which contains a layered compound and/or an oxygen storage material as an active ingredient.

Examples

The present invention will be described in detail with reference to examples. However, the present invention is not limited to the embodiment. Further, the viscosity of the obtained silsesquioxane derivative was measured at 25 ℃ using an E-type viscometer.

In the following description, parts and% denote parts by mass and% by mass.

Example 1

(preparation of silsesquioxane derivative-containing composition and cured product thereof)

70 parts of a silsesquioxane derivative having a methacryloyl group in a T unit (manufactured by Toyo Kagaku K.K., MAC-SQ TM-100, viscosity 4000 mPas), 30 parts of talc (Japanese talc, SG95, D50 ═ 2.5 μm), and 0.7 part of a thermal radical initiator (Japanese fat, PERBUTYL E, T-butylperoxy-2-ethylhexyl monocarbonate) were weighed in a vial, and mixed at 1800rpm for 1 minute using a rotary-revolving mixer to obtain a composition of test example 1.

The composition of test example 1 was applied to a sandblasted aluminum plate, and the plate was similarly bonded to the sandblasted aluminum plate, heated at 120 ℃ for 1 hour (DK 63, manufactured by Yamato Scientific), and then heated at 150 ℃ for 1 hour for thermosetting to obtain a test piece of test example 1.

The test pieces were kept in air at 350 ℃ for 1 hour, 24 hours and in a nitrogen atmosphere at 350 ℃ for 24 hours, and the tensile shear strength was measured on the test pieces before the temperature treatment and after cooling to room temperature.

The tensile shear strength of the test piece was measured using Strogaph 20-C manufactured by Toyo Seiki Seisaku-Sho. Further, the tensile shear was measured with respect to the test piece under heating at 200 ℃. The drawing speed was set to 10 mm/min. The results are shown in Table 1.

As a control, a composition was prepared in the same manner as in test example 1 using only the silsesquioxane derivative, and a test piece was prepared to prepare the test piece of comparative example a. Further, a composition comprising bisphenol A type epoxy resin and talc (75 parts: 25 parts) was prepared, and using this composition, after 1 hour at 120 ℃, it was cured for 1 hour at 150 ℃ to obtain a test piece of comparative example B. The test pieces of comparative examples 1 and 2 were subjected to the same temperature treatment, and the tensile shear strength was measured for the test pieces before and after the treatment. The results are shown together in Table 1.

[ TABLE 1]

Heating conditions	Test example 1	Comparative example A	Comparative example B
				Just after curing	5.6	3.9	16.2
350 ℃ for 1 hour	5.3(-5.4％)	2.0(-48.7％)	1.7(-89.5％)
				350 ℃ for 24 hours	0.9(-83.9％)
350 ℃ for 24 hours, N2	5.6(0)
				Heating at 200 deg.C	3.7(-33.9％)	2.3(-41.0％)	4.4(-72.8％)

As shown in table 1, the test piece (test example 1) prepared from the silsesquioxane derivative containing talc was excellent in suppressing the decrease in tensile shear strength, that is, the decrease in adhesive strength in the test piece, even when heated at 350 ℃ for 1 to several hours in air. In contrast, the silsesquioxane derivative without talc (comparative example a) and the test piece prepared from the mixed composition of the epoxy resin and talc (comparative example B) showed a significant decrease in tensile shear strength.

Example 2

(thermal behavior of silsesquioxane derivative-containing composition)

(preparation of silsesquioxane derivative (liquid, uncured curable composition)

70 parts of the same silsesquioxane derivative (MAC-SQ TM-100) as used in example 1 and 30 parts of talc (three of japanese talc, D50 ═ 1 μm, 2.5 μm, and 5 μm) were mixed to prepare 3 curable compositions (liquid).

(preparation of silsesquioxane derivative (cured product) composition)

Thermosetting composition a was prepared in the same manner as in example 1 by using 70 parts of silsesquioxane derivative (MAC-SQTM-100), 30 parts of talc (SG25, japan talc, D50 ═ 2.5 μm), and 0.7 part of thermal radical initiator (japan oil and fat, PERBUTYL E), and applied to a sandblasted aluminum plate, and heated at 120 ℃ for 1 hour (DK 63, manufactured by Yamato Scientific co., ltd.) and then further heated at 150 ℃ for 1 hour to be thermally cured to obtain cured product a.

Further, the same silsesquioxane derivative, talc (SG95), and ceria-zirconia composite oxide (average particle diameter 5 to 10nm) were each added in a mass ratio of 7: 3: 1 while mixing 0.7 part of a thermal radical initiator (Japanese fat and oil, PERBUTYL E), a thermosetting composition B was prepared in the same manner as in example 1, and the mixture was thermally cured in the same manner as in the thermosetting composition B to obtain a cured product B.

Further, a comparative thermosetting composition was prepared by applying the same silsesquioxane derivative and 0.7 parts of a radical initiator (japanese fat and oil, PERBUTYL E) to a sandblasted aluminum plate, heating the composition at 120 ℃ for 1 hour (DK 63, manufactured by Yamato Scientific co., ltd.), and further heating the composition at 150 ℃ for 1 hour to heat-cure the composition, thereby obtaining a comparative cured product, in the same manner as in example 1.

(evaluation of thermal behavior)

The thermal behaviour of only 3 liquid compositions MAC-SQ TM-100 was evaluated by TGA. The results are shown in figure 1, compositions were prepared and TGA was used to evaluate thermal behavior for these compositions. Furthermore, the thermal behavior of the cured product of bisphenol a epoxy resin was also evaluated. The results are shown in FIG. 1. In addition to the measured values of the mass change (%) of each composition, fig. 1 also shows the mass change of the silsesquioxane derivative not containing talc, which is obtained by multiplying the mass reduction of the silsesquioxane derivative by 0.7 to match the actual weight change rate of the silsesquioxane derivative with the composition.

The thermal behavior of cured A, B and the control cured were evaluated by TGA. The results are shown in FIG. 2. Fig. 2 (a) shows the rate of change in weight of 0 to 1000 ℃, and fig. 2 (b) shows the rate of change in weight enlarged over a temperature range of 300 to 600 ℃.

As shown in fig. 1, it is understood that the addition of talc shifts the weight reduction initiation temperature of the silsesquioxane derivative-containing composition (liquid, uncured curable composition) to the high temperature side, and shifts the polymerization reduction temperature to 20 ℃ or higher than that of the bisphenol a epoxy resin. Further, the talc has an average particle diameter of 1 to 5 μm, and is shifted to a high temperature side by a weight reduction temperature. In these compositions, TGA was also carried out in nitrogen, and as a result, the presence or absence of talc was not different.

As shown in fig. 2, it is also found that the polymerization reduction initiation temperature indicating oxidation also shifts to the high temperature side with respect to the silsesquioxane derivative cured product.

From the above, it is understood that the reason why the heat resistance is improved by the layered compound such as talc and/or the oxygen storage material is to suppress oxidation of the silsesquioxane derivative (uncured) and the cured product thereof. Further, it is found that oxidation is further suppressed by the addition of an oxygen storage material such as ceria-zirconia composite oxide in addition to talc.

Example 3

(test examples 1 to 17 of cured products of silsesquioxane derivatives and layered Compounds and/or oxygen storage Material)

The composition and test piece of test example 1 were prepared in the same manner as in example 1. In addition, compositions of test examples 1 to 17 were prepared and test pieces were prepared in the same manner as in test example 1 of example 1 except that the components shown in the following table were used in each part.

(silsesquioxane derivatives alone or silsesquioxane derivatives and other components of the cured product of comparative examples 1 ~ 3)

Compositions and test pieces of comparative examples 2 and 3 were prepared in the same manner as in test example 1 of example 1, except that the composition of comparative example 1 and the test piece were prepared in the same manner as in example 1, and the components of the table shown below were used.

(epoxy resin cured comparative examples 4 to 5)

Compositions and test pieces of comparative examples 4 and 5 were prepared in the same manner as in example 1 with respect to comparative example 2.

Some of these test pieces were heated at 350 ℃ for 1 hour. In addition, some of the test pieces were heated at 200 ℃ for 95 hours, 430 hours, and 1000 hours. Heating was carried out in the same manner as in example 1 using DK63 manufactured by Yamato Scientific Co. In addition, some of the test pieces were heated at 250 ℃ for 95 hours, 430 hours, and 1000 hours.

Tensile shear strength test was conducted on the test pieces before and after the temperature treatment in accordance with example 1. Further, a tensile shear test was also conducted in heating at 200 ℃ for a part of the test pieces. The results are shown in Table 2.

[ TABLE 2]

The following description will be made with respect to expressions in the table.

MAC-SQ TM-100: methacryloyl group-containing radically curable silsesquioxane derivative (manufactured by Toyo Synthesis Co., Ltd.)

AC-SQ TA-100: acryloyl group-containing radically curable silsesquioxane derivative (manufactured by Toyo Synthesis Co., Ltd.)

Epoxy resin: bisphenol A epoxy resin

TALC SG 95: talc (layered magnesium silicate Compound), D50 ═ 2.5 μm (manufactured by Nippon Talc Co., Ltd.)

TALC SG 2000: talc (layered magnesium silicate Compound), D50 ═ 1 μm (manufactured by Nippon Talc Co., Ltd.)

TALC P-3: talc (layered magnesium silicate Compound), D50 ═ 5 μm (manufactured by Nippon Talc Co., Ltd.)

Hexagonal boron nitride: hBN (Wako hBN), average particle diameter 2 to 3 μm (manufactured by Wako pure chemical industries, Ltd.)

Ceria-zirconia composite oxide: CeO (CeO)₂/ZrO₂And an average particle diameter of 5 to 10nm

Cerium oxide 1: CeO (CeO)₂And an average particle diameter of 5 to 10nm

Cerium oxide 2: CeO (CeO)₂Average particle diameter of 5.5 μm

Zirconium oxide: ZrO (ZrO)₂And an average particle diameter of 10 to 15nm

Iron oxide: fe₂O₃An average particle diameter of 50nm or less

PERBUTYL E: t-butylperoxy-2-ethylhexyl monocarbonate (manufactured by Nippon fat Co., Ltd.)

D50 of talc was prepared using SALD200 (manufactured by Shimadzu corporation) using a dispersion in which talc was dispersed by ultrasonic waves. A commercially available particle size distribution measuring apparatus by a laser diffraction/scattering method can be used. The average particle size of the hexagonal boron nitride was also D50 measured based on the particle size distribution obtained by the laser diffraction/scattering method.

As for the average particle diameters of the ceria-zirconia composite oxide, ceria 1, zirconia and iron oxide, the average particle diameter was determined by using nitrogen (N)₂) Specific surface area (m) obtained by analyzing gas adsorption amount measured by gas adsorption method as adsorbate by BET method (multipoint method)²G, S) were calculated to obtain the average particle diameter. In the measurement of the nitrogen adsorption amount, each sample was degassed at 300 ℃ for 12 hours or more under vacuum, and then subjected to gas adsorption at 77K. Furthermore, for cerium oxide2, the particle size was measured by a laser diffraction/scattering method in the same manner as talc.

As shown in table 2, the test pieces (test examples 1 to 5) obtained by bonding a silsesquioxane derivative cured product cured by containing only a lamellar compound, the test pieces (test examples 6 to 16) obtained by bonding a derivative cured product cured by containing a lamellar compound and an oxygen storage material, and the test piece (test example 17) obtained by bonding a derivative cured product cured by containing only an oxygen storage material were excellent before and after the temperature treatment and suppressed the decrease in tensile shear strength. Among them, it is understood that when the change rate of the tensile shear strength after the heat treatment at 350 ℃ for 1 hour in test examples 1 to 17 is compared with the change rate of comparative example 1 in which only the cured silsesquioxane derivative is cured, comparative examples 2 to 3 in which the cured silsesquioxane derivative containing other components is used, and comparative example 4 in which an epoxy resin is used, the decrease of the tensile shear strength at 350 ℃ in the test pieces of the test examples using the layered compound and/or the oxygen storage material is favorably suppressed. Even if silica, calcium carbonate, or the like is added, the addition is the same as that in which no silica, calcium carbonate, or the like is added. It was confirmed that a cured product was obtained in the same manner as in test example 1 for each of mica and montmorillonite which are minerals that are one kind of layered compound, and the adhesive strength was measured in the same manner, and as a result, the effect of adding a layered compound was obtained.

Further, it is understood from test examples 6 to 16 which contain both the layered compound and the oxygen storage material that the inclusion of both is effective for suppressing the decrease in tensile shear strength after heat treatment (heat resistance), and they exert a synergistic effect. Further, it was found that a high heat resistance effect was obtained even when the glass was kept at 350 ℃ for 1 hour or at 200 ℃ or 250 ℃ for a long period of time. Further, it is found that the polymerizable functional group, even if it is a methacryloyl group, has substantially the same effect of improving heat resistance as the silsesquioxane derivative having an acryloyl group.

Furthermore, as shown in test examples 1 to 5, it is also found that the layered compound exhibits a heat resistance effect in the range of, for example, 5% to 50%, preferably 10% to 40%, and more preferably 20% to 40% with respect to the total mass of the silsesquioxane derivative and the layered compound, because a sufficient effect is obtained by using 3 parts with respect to 7 parts of the silsesquioxane derivative. Further, as shown in test examples 6 to 17, it was found that the oxygen storage material is effective at 0.007% or more, more effective at 0.4% or more, further effective at 10% or more, and further effective at 20% or more, based on the total mass of the silsesquioxane derivative and the oxygen storage material, for example. Further, the adhesive strength was sufficient even when the amount of the adhesive was 30%. From the above, it is understood that the oxygen storage material may be set to, for example, 0.07% or more and 30% or less, preferably 0.4% or more and 20% or less, or the like, relative to the total mass of the silsesquioxane derivative and the oxygen storage material. Further, in the case where the layered compound and the oxygen storage material are contained, it is found that sufficient adhesive strength can be maintained even if the total mass of the silsesquioxane derivative, the groove-like compound, and the oxygen storage material is more than 40%.

The oxygen storage material exhibits a heat-resistant effect on the silsesquioxane derivative cured product, but does not sufficiently exhibit a heat-resistant effect on the epoxy resin.

From the above, it is understood that these effects of the layered compound and the oxygen storage material more effectively act on the silsesquioxane derivative or a cured product thereof.

Further, it is found that both talc and hexagonal boron nitride, which are layered compounds, exhibit excellent heat resistance, and that the heat resistance is greater when the average particle size is small. That is, if the average particle diameter is larger than 5 μm, the effect of improving the heat resistance tends to be uneven. Therefore, it is found that the lamellar compound is suitable for a lamellar compound having an average particle diameter of less than 5 μm, preferably 4 μm or less, and more preferably 3 μm or less.

Further, it is understood from examples 1 to 5 and comparative example 1 that the oxygen storage material exhibits a higher heat resistance. Among the oxygen storage materials, ceria-zirconia composite oxides having high oxygen storage capacity are known to have the highest oxidation resistance. Further, it is found that if the average particle size of the oxygen storage material is larger than 5 μm, the oxidation resistance tends to be lowered, and the average particle size of the oxygen storage material is preferably smaller than 5 μm, more preferably 4 μm or smaller, further preferably 3 μm or smaller, still more preferably 2 μm or smaller, and further preferably 1 μm or smaller.

Example 4

(thermal behavior of cured composition of other silsesquioxane derivative)

As the silsesquioxane derivative, the following compounds were used in SiO_1.5Silsesquioxane derivatives having an oxetanyl group in a unit (OX-SQ, TX-100, Toyo Synthesis Co., Ltd., hereinafter referred to as silsesquioxane A) and SiO 2 shown below in the same manner_1.5Silsesquioxane derivatives having epoxy groups in the unit (hereinafter referred to as silsesquioxane B, manufactured by east asian corporation) were prepared using talc (SG95) and ceria-zirconia composite oxide (average particle diameter 5 to 10nm), each in a mass ratio of 7: 3: 1 to prepare compositions (liquid), and the thermal behavior of these compositions was evaluated by TGA. TGA was similarly performed for only silsesquioxanes a and B. The results are shown in FIG. 3. In fig. 3, the change in mass of the silsesquioxane A, B that cancels out the presence of talc or the like in the composition is shown by multiplying the change in mass by 0.63 based on the measured value of the change in mass (%) of the silsesquioxane A, B.

[ chemical formula 6]

As shown in fig. 3, it is understood that the addition of talc and ceria-zirconia composite oxide shifts the weight loss initiation temperature of the silsesquioxane derivative curing oxidation to the high temperature side.

From the above, it is found that the layered compound and the oxygen storage material achieve the oxidation inhibiting effect and the heat resistance effect in the same manner in the silsesquioxane cured product having the polymerizable functional group.