KR102640556B1 - Silsesquioxane derivative composition and use thereof - Google Patents

Abstract

In order to improve the heat resistance of silsesquioxane derivatives, a silsesquioxane derivative composition containing a silsesquioxane derivative and a layered compound is provided.

Description

Silsesquioxane derivative composition and use thereof

This specification relates to compositions containing silsesquioxane derivatives and their uses.

(Cross-reference to related applications)

This application is a related application to Japanese Patent Application No. 2018-196951, filed on October 18, 2018, priority is claimed based on this Japanese application, and all contents described in this Japanese application are included.

Silsesquioxane is a compound having a three-dimensional cross-linked structure by siloxane bonds having the unit represented by RSiO _1.5 as a structural unit, and R may have various functional groups including an organic functional group. These silsesquioxane derivatives (silsesquioxane derivatives) are known as materials with excellent heat resistance (Patent Documents 1 and 2). Additionally, since silsesquioxane derivatives are inorganic-organic hybrid materials, they can exhibit organic properties such as flexibility and solubility in addition to inorganic properties such as heat resistance. For example, certain types of silsesquioxane derivatives have polymerizable functional groups such as epoxy groups as organic groups and are therefore used as curable adhesives (Patent Document 3).

International Publication No. 2005/10077 International Publication No. 2009/66608 Japanese Patent Publication No. 2018-95819

According to the present inventors, depending on conditions such as atmosphere and heating temperature, the organic groups included in the silsesquioxane derivative are oxidized, which causes the original silsesquioxane derivative to deteriorate, for example, in mechanical properties at high temperatures. It was found that the properties of quinoxane sometimes change.

However, no technology has been reported to suppress oxidation of organic groups in silsesquioxane. Additionally, since silsesquioxane is known to have high heat resistance, no effective technology has been provided to further improve the heat resistance. Moreover, the current situation is that technologies for securing heat resistance under harsh conditions where organic groups in silsesquioxane are oxidized are not even being considered.

This specification provides a technology for enhancing heat resistance by suppressing oxidation of silsesquioxane and its use.

The present inventors focused on the possibility of the existence of additives that can suppress the oxidation of organic groups in silsesquioxane derivatives and searched for such additives. As a result, it was found that both the layered compound and the oxygen storage material can suppress the oxidation of the silsesquioxane derivative, and as a result, the heat resistance of the silsesquioxane derivative can be improved. This specification provides the following means based on their knowledge.

[1] Silsesquioxane derivatives,

Silsesquioxane derivative composition containing layered compounds.

[2] The composition according to [1], wherein the layered compound is one or two or more types selected from the group consisting of 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], which contains the layered compound in an amount of 5% by mass or more and 50% by mass or less relative to the total mass of the silsesquioxane derivative and the layered compound.

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

[7] Silsesquioxane derivatives,

A silsesquioxane derivative composition containing an oxygen storage material.

[8] The composition according to [6] or [7], wherein the oxygen storage material is one or two or more types selected from the group consisting of ceria, zirconia, and ceria-zirconia composite oxide.

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

[10] The composition according to any one of [6] to [9], which contains the oxygen storage material in an amount of 0.1% by mass or more and 40% by 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 silsesquioxane derivative having a polymerizable functional group,

A curable silsesquioxane derivative composition comprising a layered compound and/or an oxygen storage material.

[13] A cured product of a silsesquioxane derivative having a polymerizable functional group,

A silsesquioxane derivative cured composition comprising 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 a step of heating the silsesquioxane derivative together with a layered compound and/or an oxygen storage material.

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

[16] An oxidation inhibitor of a silsesquioxane derivative or a cured product thereof containing a layered compound and/or an oxygen storage material as an active ingredient.

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

1 is a diagram showing the thermal behavior of a silsesquioxane derivative having a methacryloyl group.
Figure 2 is a diagram showing the thermal behavior of a cured product of a silsesquioxane derivative.
Figure 3 is a diagram showing the thermal behavior of other silsesquioxane derivatives having an oxetanyl group and an epoxy group.

The disclosure of this specification relates to a technology for further improving the heat resistance of silsesquioxane derivatives by imparting oxidation resistance to the silsesquioxane derivative. According to the disclosure of this specification, the presence of a layered compound can suppress oxidation of the silsesquioxane derivative and further improve the stability of the silsesquioxane derivative, particularly stability against heat (heat resistance). The reason why this effect occurs due to the layered compound is not necessarily clear. It is thought that the gas barrier properties and gas diffusion inhibition properties of the layered compound are involved in suppressing oxidation of organic groups.

The disclosure of the present specification also suppresses oxidation of the silsesquioxane derivative and further improves the stability of the silsesquioxane derivative, particularly stability against heat (heat resistance), by the presence of an oxygen storage material. This action is thought to be due to self-oxidation/reduction or adsorption of oxygen by the oxygen storage material.

Silsesquioxane derivatives may have various organic groups, but for example, they may have polymerizable functional groups. When these silsesquioxane derivatives are polymerized, decomposition due to oxidation of their polymerizable functional groups may have a significant impact on the characteristics of the silsesquioxane derivative. Therefore, it is significant that oxidation resistance is imparted to the silsesquioxane derivative composition containing the silsesquioxane derivative having such a functional group and the cured product obtained from the composition by the layered compound and/or the oxygen storage material. .

Hereinafter, representative and non-limiting embodiments of the present disclosure will be described in detail with appropriate reference to the drawings. This detailed description is simply intended to show those skilled in the art the details for carrying out preferred examples of the present disclosure, and is not intended to limit the scope of the present disclosure. Additionally, the additional features and inventions disclosed below can be used separately or together with other features or inventions to provide a further improved “silsesquioxane derivative composition and use thereof.”

In addition, combinations of features and processes disclosed in the detailed description below are not essential for practicing the present disclosure in the broadest sense, and are specifically described only to explain representative embodiments of the present disclosure. Additionally, various features of the representative embodiments above and below, and those recited in independent and dependent claims, may be used as embodiments described herein, or in the order in which they are listed, in providing additional and useful embodiments of the present disclosure. It doesn't mean you have to combine them.

All features described in the specification and/or claims are intended to be disclosed individually and independently of each other, as a limitation to the original disclosure of the application and to the specific matters claimed, separately from the configuration of the features described in the examples and/or claims. will be. In addition, all descriptions of numerical ranges and groups or populations are intended to disclose the original disclosure of the application and any intermediate structures thereof as a limitation to the specific matters claimed.

Hereinafter, the technology for inhibiting oxidation of silsesquioxane derivatives according to the present disclosure and various embodiments of its use will be described. Specifically, a silsesquioxane derivative composition, a silsesquioxane derivative cured product composition, a method for inhibiting oxidation or heat resistance of silsesquioxane, an oxidation inhibitor or heat resistance improver for silsesquioxane, etc. will be described.

(Silsesquioxane derivative composition)

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

(silsesquioxane derivative)

In this specification, silsesquioxane is a polysiloxane whose main chain skeleton consists of Si-O bonds and (RSiO _1.5 ) units. The silsesquioxane derivative in the present specification is a compound comprising such polysiloxane and one or two or more units represented by (RSiO _1.5 ) (T unit).

For example, silsesquioxane derivatives have the following formula (1) comprising structural units (1-1), (1-2), (1-3), (1-4) and (1-5). It can be expressed as In formula (1), v, w, x, y, and z each represent the number of moles of structural units (1-1) to (1-5). In addition, in formula (1), v, w, x, y and z mean the average value of the ratio of the number of moles of each structural unit contained in one molecule of silsesquioxane derivative.

Each of the structural units (1-2) to (1-5) in formula (1) may be of one type or may be of two or more types. In addition, the condensation form of the actual structural units of the silsesquioxane derivative is not limited to the arrangement order represented by formula (1) and is not particularly limited.

Silsesquioxane derivatives have five structural units in formula (1), namely structural unit (1-1), structural unit (1-2), structural unit (1-3), and structural unit (1-4). The structural units selected from can be provided in combination to include at least one polymerizable functional group.

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

<Constitutive unit (1-1): Q unit>

This structural unit is as expressed in formula (1), and defines the Q unit as the basic structural unit of polysiloxane. The number of structural units in the silsesquioxane derivative is not particularly limited.

<Constitutive unit (1-2): T unit>

This structural unit specifies the T unit as the basic structural unit of polysiloxane. R ¹ of this structural unit is a hydrogen atom, an alkyl group of 1 to 10 carbon atoms (hereinafter also referred to as a C _1-10 alkyl group), an alkenyl group of 1 to 10 carbon atoms, or an alkyl group of 1 to 10 carbon atoms. It can be at least one type selected from the group consisting of a nyl group, an aryl group, an aralkyl group, and a polymerizable functional group.

R ¹ may be a hydrogen atom. In the case of a hydrogen atom, for example, this structural unit and/or other structural units are organic groups of 2 to 10 carbon atoms containing a hydrosilylation-reactive carbon-carbon unsaturated bond contained in a polymerizable functional group (hereinafter, only In the case where it is provided with an unsaturated organic group (also called an unsaturated organic group), a crosslinking reaction becomes possible between these units.

R ¹ is C _1-10 It may be an alkyl group. The C _1-10 alkyl group may be either an aliphatic group or an alicyclic group, and may be either linear or branched. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group. Such alkyl groups are straight-chain alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups, and also include, for example, methyl, ethyl, propyl, and butyl groups. It is a straight-chain alkyl group with 1 to 4 carbon atoms. Also, for example, it is a methyl group.

R ¹ may be a C _1-10 alkenyl group. The C _1-10 alkenyl group may be any of an aliphatic group, an alicyclic group, or an aromatic group, and may also be either linear or branched. Specific examples of alkenyl groups include ethenyl (vinyl) group, orthostyryl group, metastyryl group, parastyryl group, 1-propenyl group, 2-propenyl (allyl) group, 1-butenyl group, 1-pentenyl group, 3- Examples include methyl-1-butenyl group, phenylethenyl group, allyl (2-propenyl) group, and octenyl (7-octen-1-yl) group.

R ¹ may be a C1-10 alkynyl group. The C _1-10 alkynyl group may be any of an aliphatic group, an alicyclic group, and an aromatic group, and may also be either linear or branched. Specific examples of the alkynyl group include ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 3-methyl-1-butynyl group, and phenylbutynyl group.

R ¹ may be an aryl group. The number of carbon atoms is, for example, 6 to 20, and for example, is 6 to 10. Examples of the aryl group include phenyl group, 1-naphthyl group, and 2-naphthyl group.

R ¹ may be an aralkyl group. The number of carbon atoms is, for example, 7 to 20, and, for example, is 7 to 10. Examples of the aralkyl group include phenyl alkyl groups such as benzyl group.

R ¹ may be a polymerizable functional group. Examples of the polymerizable functional group include polymerizable functional groups that can be heat-cured or photo-cured. The polymerizable functional group is not particularly limited and includes the above-mentioned functional groups such as vinyl group, allyl group, and styryl group, but also includes methacryloyl group, acryloyl group, acryloyloxy group, methacryloyloxy group, and α-methyl. Styryl group, vinyl ether group, vinyl ester group, acrylamide group, methacrylamide group, N-vinylamide group, maleic acid ester group, fumaric acid ester group, N-substituted maleimide group, isocyanate group, oxetanyl group, and A functional group having an epoxy group, etc. can be mentioned. Among them, polymerizable functional groups having a (meth)acryloyl group, oxetanyl group, and epoxy group can be mentioned.

As the polymerizable functional group having a (meth)acryloyl group, for example, a group represented by the following formula or a group containing this group is preferable.

In the above formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkylene group having 1 to 10 carbon atoms. As R ⁶ , an alkylene group having 2 to 10 carbon atoms is preferable.

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

In the above formula, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁸ represents an alkylene group having 1 to 6 carbon atoms. As R ⁷ , a hydrogen atom, a methyl group, or an ethyl group is preferable, and an ethyl group is more preferable. As R ⁸ , an alkylene group having 2 to 6 carbon atoms is preferable, and a propylene group is more preferable.

The epoxy group is not particularly limited, but includes, for example, an alkyl group having 1 to 10 carbon atoms substituted with a glycidoxy group such as β-glycidoxyethyl, γ-glycidoxypropyl, or γ-glycidoxybutyl, a glycidyl group, β-(3,4-epoxycyclohexyl)ethyl group, γ-(3,4-epoxycyclohexyl)propyl group, β-(3,4-epoxycyclobutyl)ethyl group, 4-(3,4-epoxycyclohexyl) )Alkyl groups of 1 to 10 carbon atoms substituted with cycloalkyl groups of 5 to 8 carbon atoms with an oxirane group such as butyl group and 5-(3,4-epoxycyclohexyl)pentyl group.

The polymerizable functional group may be an unsaturated organic group as previously described, that is, a functional group having a hydrogen atom (hydrosilyl group) bonded to a silicon atom and a carbon-carbon double bond or carbon-carbon triple bond capable of hydrosilylation. The unsaturated organic group can also function as a polymerizable functional group in the sense that, due to the presence of a hydrogen atom in the hydrosilyl group, it polymerizes with the hydrogen atom through a hydrosilylation reaction to form a hydrosilylated structural moiety. Specific examples of such unsaturated organic groups include the alkenyl group and alkynyl group described above. Although not particularly limited, examples include vinyl group, orthostyryl group, metastyryl group, parastyryl group, acryloyl group, methacryloyl group, acryloxy group, methacryloxy group, 1-propenyl group, 1-butylene group. Nyl group, 1-pentenyl group, 3-methyl-1-butenyl group, phenylethenyl group, ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 3-methyl-1-butynyl group, phenylbuty Nyl group, allyl (2-propenyl) group, octenyl (7-octen-1-yl) group, etc. are exemplified. Such unsaturated organic groups include, for example, vinyl group, parastyryl group, allyl (2-propenyl) group, octenyl (7-octen-1-yl) group, and further examples include vinyl group.

In addition, the entire silsesquioxane derivative may contain two or more types of polymerizable functional groups. In that case, all polymerizable functional groups may be the same or different from each other. In addition, a plurality of polymerizable functional groups may be the same or may contain different polymerizable functional groups.

The C _1-10 alkyl group, C _1-10 alkenyl group, and C _1-10 alkynyl group may all be substituted as aryl group, aralkyl group, and polymerizable functional group. Such substituents include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and chlorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, and t-butyl group. , alkyl groups such as n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, hydroxy group, alkoxy group, aryloxy group, aralkyloxy group, and oxy group (=O), cyano group. , it may be substituted with at least one of the protected hydroxyl groups.

The protecting group of the hydroxyl group possessed by the protected hydroxyl group is not particularly limited, and a known hydroxyl protecting group can be used. For example, such a protecting group includes an acyl-based protecting group represented by -C(=O)R (wherein R is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s). -Alkyl group having 1 to 6 carbon atoms such as butyl group, t-butyl group, n-pentyl group, etc. Or phenyl group with or without substituent. Examples of substituents for phenyl group with substituent include methyl group, ethyl group, n- Propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, etc. Alkyl group; Halogen atom such as fluorine atom, chlorine atom, bromine atom, etc.; Alkoxy group such as methoxy group, ethoxy group, etc.), trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group Silyl-based protecting groups such as; Acetal-based protecting groups such as methoxymethyl group, methoxyethoxymethyl group, 1-ethoxyethyl group, tetrahydropyran-2-yl group, and tetrahydrofuran-2-yl group; Alkoxycarbonyl-based protecting groups such as t-butoxycarbonyl group; Ether-based protecting groups such as methyl group, ethyl group, t-butyl group, octyl group, allyl group, triphenylmethyl group, benzyl group, p-methoxybenzyl group, fluorenyl group, trityl group, and benzhydryl group, etc. there is.

Silsesquioxane derivatives can be prepared by combining one type or two or more types of this structural unit. For example, R ¹ of one structural unit can be an alkyl group, and R ¹ of the other structural unit can be a polymerizable function. Additionally, for example, R ¹ of one structural unit may be a hydrogen atom, and R ¹ of the other structural unit may be an unsaturated organic group as a polymerizable functional group.

w, which is the ratio of the number of moles of this structural unit in the silsesquioxane derivative, is a positive number. w is not particularly limited, but for example w/(v+w+x+y) is 0.25 or more, for example 0.3 or more, for example 0.35 or more, and for example 0.4 or more. , for example, 0.5 or more, for example, 0.6 or more, for example, 0.7 or more, for example, 0.8 or more, for example, 0.9 or more, and for example, 0.95 or more. For example, it is 0.99 or more, and for example, it is 1.

<Constitutive unit (1-3): D unit>

This structural unit specifies the D unit as the basic structural unit of silsesquioxane derivatives. R ² of this structural unit is at least one selected from the group consisting of a hydrogen atom, C _1-10 alkyl group, C _1-10 alkenyl group, C _1-10 alkynyl group, aryl group, aralkyl group, and polymerizable functional group. You can. R ² in this structural unit may be the same or different.

The various aspects already described for the C _1-10 alkyl group, C _1-10 alkenyl group, C _1-10 alkynyl group, aryl group, aralkyl group, and polymerizable functional group can also be applied to the present structural unit.

Silsesquioxane derivatives can be prepared by combining one type or two or more types of this structural unit. In the silsesquioxane derivative, at least some of the structural units, for example, both R ² are C _1-10 alkyl groups, and for example, all of the structural units, both R ² are C _{1-10 alkyl} groups. It is an alkyl group.

x, which is the ratio of the number of moles of this structural unit in the silsesquioxane derivative, is 0 or a positive number. x is not particularly limited, but for example x/(v+w+x+y) is 0.25 or more, for example 0.3 or more, for example 0.35 or more, and for example 0.4 or more. . This numerical value is, for example, 0.5 or less, and for example, is 0.45 or less.

<Constitutive unit (1-4): M unit>

This structural unit defines the M unit as the basic structural unit of silsesquioxane derivatives. R ³ of this structural unit is at least one selected from the group consisting of a hydrogen atom, C _1-10 alkyl group, C _1-10 alkenyl group, C _1-10 alkynyl group, aryl group, aralkyl group, and polymerizable functional group. You can. It can be at least one type selected from the group consisting of a hydrogen atom, a polymerizable functional group, and a C _1-10 alkyl group. R ³ in this structural unit may be the same or different.

The various aspects already described for the C _1-10 alkyl group, C _1-10 alkenyl group, C _1-10 alkynyl group, aryl group, aralkyl group, and polymerizable functional group can also be applied to the present structural unit.

Silsesquioxane derivatives can be prepared by combining one type or two or more types of this structural unit. In the silsesquioxane derivative, at least some of the structural units, for example, both R ³ are C _1-10 alkyl groups, and for example, all of the structural units, both R ³ are C _{1-10 alkyl} groups. It is an alkyl group.

y, which is the ratio of the number of moles of this structural unit in the silsesquioxane derivative, is 0 or a positive number. y is not particularly limited, but for example y/(v+w+x+y) is 0.25 or more, for example 0.3 or more, for example 0.35 or more, and for example 0.4 or more. . This numerical value is, for example, 0.5 or less, and for example, is 0.45 or less.

<Constitutive units (1-5)>

This structural unit defines a unit containing an alkoxy group or hydroxyl group in a silsesquioxane derivative. That is, R ⁴ in this structural unit is 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, and may be either linear or branched. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, and hexyl group. Typically, it is an alkyl group with 2 to 10 carbon atoms, such as a methyl group, ethyl group, n-propyl group, and isopropyl group, and also, for example, an alkyl group with 1 to 6 carbon atoms.

The alkoxy group in this structural unit is an "alkoxy group" which is a hydrolyzable group contained in the raw material monomer described later, or an "alkoxy group" produced by substituting the hydrolyzable group of the raw material monomer with the alcohol contained in the reaction solvent, and is hydrolyzed... It remains in the molecule without polycondensation. In addition, the hydroxyl group in this structural unit is a hydroxyl group or the like that remains in the molecule without polycondensation of the “alkoxy group” after hydrolysis.

z, which is the ratio of the number of moles of this structural unit in the silsesquioxane derivative, is 0 or a positive number.

In the silsesquioxane derivative, it is preferable to include one or two or more types selected from the group consisting of structural unit (1-1), structural unit (1-3), and structural unit (1-4). That is, in equation (1), it is preferable that one or two or more of v, x, and y are positive numbers.

<Molecular weight, etc.>

The number average molecular weight of the silsesquioxane derivative is preferably in the range of 300 to 10,000. These silsesquioxane derivatives themselves have low viscosity, are easily soluble in organic solvents, and the viscosity of the solution is easy to handle and has excellent storage stability. Considering applicability, storage stability, heat resistance, etc., the number average molecular weight is preferably 300 to 8,000, more preferably 300 to 6,000, further preferably 300 to 3,000, further preferably 300 to 2,000, further preferably. is 500 to 2,000. The number average molecular weight can be determined by GPC (gel permeation chromatography), for example, under the measurement conditions in the [Examples] described later, using polystyrene as a standard material.

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

<Method for producing silsesquioxane derivatives>

Silsesquioxane derivatives can be produced by known methods. Methods for producing silsesquioxane derivatives are described in International Publication No. 2005/010077 Pamphlet, International Publication No. 2009/066608 Pamphlet, International Patent Publication No. 2013/099909 Pamphlet, Japanese Patent Publication No. 2011-052170, and Japanese Patent Publication No. 2013-147659. A method for producing polysiloxane is disclosed in detail in publications and the like.

Silsesquioxane derivatives can be produced, for example, by the following method. That is, the method for producing a silsesquioxane derivative may include a condensation step in which a hydrolysis/polycondensation reaction of the raw material monomer that gives the structural unit in the above formula (1) is carried out by condensation in an appropriate reaction solvent. In this condensation step, a silicon compound having four siloxane bond forming groups (hereinafter referred to as “Q monomer”) forming structural unit (1-1) and a siloxane bond forming structural unit (1-2) A silicon compound having three forming groups (hereinafter referred to as “T monomer”), and a silicon compound having two siloxane bond forming groups (hereinafter referred to as “D monomer”) forming structural unit (1-3). , a silicon compound that forms structural unit (1-4) having one siloxane bond forming group (hereinafter referred to as “M monomer”) can be used.

In this specification, specifically, the Q monomer forming structural unit (1-1), the T monomer forming structural unit (1-2), the D monomer forming structural unit (1-3), and the composition Of the M monomers forming units (1-4), at least the T monomer is used. After subjecting the raw material monomer to a hydrolysis/polycondensation reaction in the presence of a reaction solvent, it is preferable to provide a distillation removal process for distilling off the reaction solvent, by-products, residual monomers, water, etc. in the reaction solution.

The siloxane bond forming group contained in the raw material monomers Q monomer, T monomer, D monomer or M monomer is a hydroxyl group or a hydrolyzable group. Among these, hydrolyzable groups include halogeno groups and alkoxy groups. It is preferable that at least one of the Q monomer, T monomer, D monomer, and M monomer has a hydrolyzable group. In the condensation process, an alkoxy group is preferable as a hydrolyzable group because it has good hydrolyzability and does not produce an acid as a by-product, and an alkoxy group having 1 to 4 carbon atoms is more preferable.

In addition, in the synthesis of silsesquioxane derivatives, a silicone compound (hereinafter also referred to as a D oligomer) having a siloxane bond forming group represented by the following formulas (2) and (3) can be used instead of the D monomer.

^{( In} the above formulas ( ² ) and ( ³ ), ¹³ is an alkyl group, cycloalkyl group, or aryl group, respectively, and m and n are positive integers)

The siloxane bond forming group possessed by the D oligomer refers to an atom or atomic group capable of forming a siloxane bond between silicon atoms in a silane compound, and specific examples include methoxy group, ethoxy group, n-propoxy group, i- These include alkoxy groups such as propoxy groups, n-butoxy groups, i-butoxy groups, and t-butoxy groups, cycloalkoxy groups such as cyclohexyloxy groups, aryloxy groups such as phenyloxy groups, hydroxyl groups, and hydrogen atoms. The D oligomer represented by formula (2) has two siloxane bond forming groups in one molecule, but these groups may be the same or different groups.

D oligomers in which the siloxane bond forming group is a hydroxyl group are readily available.

R ⁹ and R ¹² of the D oligomer are each an alkoxy group, an aryloxy group, an alkyl group, a cycloalkyl group, or an aryl group, and two R ⁹ and R ¹² in one molecule may be the same group or different groups. Specific examples of R ⁹ and R ¹² include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, cyclohexyloxy group, and phenyloxy group. , methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, cyclohexyl group, phenyl group, etc.

R ¹⁰ , R ¹¹ and R ¹³ of the D oligomer are each an alkyl group, cycloalkyl group or aryl group, and multiple R ¹⁰ and R ¹¹ in one molecule may be the same group or different groups. Specific examples of R ¹⁰ , R ¹¹ and R ¹³ are methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, cyclohexyl group, phenyl group, etc. As the D oligomer, one in which multiple R ¹⁰ and R ¹¹ in one molecule are methyl or phenyl groups is preferable because it can be manufactured from inexpensive raw materials and the cured product obtained using the present composition has excellent adhesion, for example. And, especially, it is more preferable that all of them are methyl groups.

In the D oligomer, the repeating unit numbers m and n are positive integers, and in the D oligomer, m and n are preferably 10 to 100, and more preferably 10 to 50.

In the condensation process, the siloxane bond forming group of the Q monomer, T monomer, D monomer, or D oligomer corresponding to each structural unit is an alkoxy group, and the siloxane bond forming group contained in the M monomer is preferably an alkoxy group or a siloxy group. . In addition, the monomers and oligomers corresponding to each structural unit may be used individually, or two or more types may be used in combination.

Examples of the Q monomer that provides the structural unit (1-1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. Examples of T monomers that provide structural units (1-2) include trimethoxysilane, triethoxysilane, tripropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and methyltriisoprop. Poxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, trichlorosilane etc. can be mentioned. Examples of T monomers that provide structural units (1-2) include trimethoxyvinylsilane, triethoxyvinylsilane, vinyltris(2-methoxyethoxy)silane, trimethoxyallylsilane, triethoxyallylsilane, and trimethoxyallylsilane. Methoxy(7-octen-1-yl)silane, (p-styryl)trimethoxysilane, (p-styryl)triethoxysilane, (3-methacryloyloxypropyl)trimethoxysilane, (3-methacryloyloxypropyl)triethoxysilane, (3-acryloyloxypropyl)trimethoxysilane, and (3-acryloyloxypropyl)triethoxysilane. D monomers that provide structural units (1-3) include dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, diethoxydiethylsilane, dipropoxydimethylsilane, dipropoxydiethylsilane, and dimethoxy. Benzylmethylsilane, diethoxybenzylmethylsilane, dichlorodimethylsilane, dimethoxymethylsilane, dimethoxymethylvinylsilane, diethoxymethylsilane, diethoxymethylvinylsilane, etc. are mentioned. Examples of M monomers that give structural units (1-4) include hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, 1,1,3, which give two structural units (1-4) by hydrolysis. 3-Tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, methoxydimethylsilane, ethoxydimethylsilane, methoxydimethylvinylsilane, ethoxydimethylvinylsilane, etc. Methoxytrimethylsilane, ethoxytrimethylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorodimethylsilane, chlorodimethylvinylsilane, chlorotrimethylsilane, dimethylsilanol, dimethylvinylsilanol, trimethylsilanol, triethylsilanol , tripropylsilanol, tributylsilanol, etc. Organic compounds giving structural units (1-5) include 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, methanol, ethanol, etc. Examples include alcohol. According to the above description, compositions containing such monomers for obtaining silsesquioxane derivatives are also provided.

In the condensation process, alcohol can be used as a reaction solvent. Alcohol is an alcohol in the narrow sense represented by the general formula R-OH, and is a compound that has no functional group other than an alcoholic hydroxyl group. Although not particularly limited, specific examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 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-pentane Examples include ol, 2-ethyl-2-butanol, 2,3-dimethyl-2-butanol, and cyclohexanol. Among these, isopropyl alcohol, 2-butanol, 2-pentanol, 3-pentanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 3-methyl-2-pentanol Secondary alcohols such as cyclohexanol are used. In the condensation process, these alcohols can be used one type or in combination of two or more types. A more preferred alcohol is a compound that can dissolve water in the concentration required for the condensation process. Alcohols with these properties are compounds that have a water solubility of 10 g or more per 100 g of alcohol at 20°C.

The alcohol used in the condensation process is used in an amount of 0.5 mass% or more based on the total amount of all reaction solvents, including the additional input during the hydrolysis/polycondensation reaction, to suppress gelation of the resulting silsesquioxane derivative. . A preferable usage amount is 1% by mass or more and 60% by mass or less, and more preferably 3% by mass or more and 40% by mass or less.

The reaction solvent used in the condensation step may be alcohol alone, or may be a mixed solvent with at least one type of subsolvent. The subsolvent may be either a polar solvent or a non-polar solvent, or may be a combination of both. Preferred polar solvents include secondary or tertiary alcohols having 3 or 7 to 10 carbon atoms, diols having 2 to 20 carbon atoms, etc. In addition, when using a primary alcohol as a subsolvent, it is preferable that the amount used is 5% by mass or less of the total reaction solvent. A preferred polar solvent is 2-propanol, which can be obtained industrially and inexpensively. By using 2-propanol and the alcohol according to the present invention in combination, the alcohol according to the present invention can dissolve water at the concentration required in the hydrolysis process. Even if it is not present, the effect of the present invention can be obtained because the required amount of water can be dissolved with a polar solvent. The amount of the polar solvent is preferably 20 parts by mass or less, more preferably 1 to 20 parts by mass, particularly preferably 3 to 10 parts by mass, per 1 part by mass of the alcohol according to the present invention.

Nonpolar solvents are not particularly limited and include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, alcohols, ethers, amides, ketones, esters, cellosolves, etc. Among these, aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons are preferred. These nonpolar solvents are not particularly limited, but for example, n-hexane, isohexane, cyclohexane, heptane, toluene, xylene, and methylene chloride are preferred because they are azeotropic with water. When these compounds are used together, after the condensation step, When removing the reaction solvent by distillation from a reaction mixture containing a silsesquioxane derivative, polymerization catalysts such as moisture and acids dissolved in water can be efficiently distilled off. As a nonpolar solvent, xylene, an aromatic hydrocarbon, is particularly preferable because it has a relatively high boiling point. The amount of the non-polar solvent used is 50 parts by mass or less, more preferably 1 to 30 parts by mass, particularly preferably 5 to 20 parts by mass, per 1 part by mass of the alcohol according to the present invention.

The hydrolysis/polycondensation reaction in the condensation process proceeds in the presence of water. The amount of water used to hydrolyze the hydrolyzable group contained in the raw material monomer is preferably 0.5 to 5 times the mole, more preferably 1 to 2 times the mole, relative to the hydrolyzable group. In addition, the hydrolysis/polycondensation reaction of the raw material monomer may be performed without a catalyst or may be performed using a catalyst. Acid or alkali is used as a catalyst in hydrolysis/polycondensation reactions. Examples of such catalysts include inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid; Acid catalysts exemplified by organic acids such as formic acid, acetic acid, oxalic acid, and p-toluenesulfonic acid are preferably used. The amount of the acid catalyst used is preferably equivalent to 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 methods described in various publications, etc. as previously described. Additionally, in the condensation process for producing a silsesquioxane derivative, an auxiliary may be added to the reaction system. For example, an antifoaming agent that suppresses foaming of the reaction solution, a scale control agent that prevents scale from adhering to the reaction can or stirring shaft, a polymerization inhibitor, and a hydrosilylation reaction inhibitor. The amount of these aids used is arbitrary, but is preferably about 1 to 10% by mass relative to the concentration of the silsesquioxane derivative in the reaction mixture.

After the condensation process in the production of the silsesquioxane derivative, a distillation removal process is provided to distill off the reaction solvent, by-products, residual monomers, water, etc. contained in the reaction liquid obtained from the condensation process, thereby producing silsesquioxane. The stability and usability of oxane derivatives can be improved. In particular, the acid or base used as the polymerization catalyst can be efficiently removed by simultaneously distilling off a solvent that is azeotropic with water as the reaction solvent. In addition, although distillation removal depends on the boiling point of the solvent used, appropriate reduced pressure conditions can be used at a temperature of 100°C or lower.

(Layered compound)

The composition may contain layered compounds. The layered compound is not particularly limited, and one or two or more types of known layered compounds can be used. Examples of the layered compound include silicate layered compounds such as talc (layered magnesium silicate), boron nitride, and minerals such as mica and smectite. Among them, talc and boron nitride can be mentioned.

Layered compounds are generally in powder form. The particle shape is not particularly limited. Additionally, the average particle diameter is not particularly limited, but is preferably 10 μm or less, for example. This is because when it is 10 μm or less, good oxidation resistance is obtained. More preferably, it is 5㎛ or less. Furthermore, it is more preferably 3 μm or less, and even more preferably 2.5 μm or less. In addition, the lower limit is not particularly limited, but is, for example, 0.5 μm or more, and further, for example, is 1.0 μm or more. Additionally, the average particle diameter of the layered compound can be measured by laser diffraction/scattering method. In this specification, the average particle size of the layered compound refers to the particle size D50 corresponding to the cumulative frequency of 50% by volume from the small particle size side in the volume-based particle size distribution based on the laser diffraction/scattering method. In the measurement, a dispersion of a layered compound such as talc dispersed using ultrasonic waves can be used.

The content of the layered compound in this composition is not particularly limited, and can be set to an effective amount that suppresses oxidation of the silsesquioxane derivative used. The layered compound is, for example, 5% by mass or more, for example, 10% by mass or more, for example, 15% by mass or more, further, for example, 20% by mass, relative to the total mass of the silsesquioxane derivative and the layered compound. or more, for example, 25% by mass or more, and further, for example, 30% by mass or more. Also, with respect to the total amount of copper, it can be, for example, 50% by mass or less, further, for example, 45% by mass or less, and further, for example, 40% by mass or less. In addition, the content of the layered compound is, for example, 5% by mass or more and 50% by mass or less, for example, 10% by mass or more and 40% by mass or less, with respect to the total mass of the silsesquioxane derivative and the layered compound, for example. It can be 20 mass% or more and 40 mass% or less.

(Oxygen storage material)

The composition may include an oxygen storage material. The oxygen storage material is a material that has the ability to store oxygen. The oxygen storage material is not particularly limited, and known oxygen storage materials can be used. For example, alumina, titania, zirconia, ceria, iron oxide (Fe ₂ O ₃ ), ceria zirconia composite oxide, and any type of perovskite. A t-type metal oxide, etc. can be mentioned. Additionally, zirconia and ceria zirconia composite oxide may be stabilized with a known stabilizer. The oxygen storage material may be a metal oxide doped with another metal atom. As the oxygen storage material, for example, ceria, zirconia, and ceria-zirconia composite oxide can be preferably used. The oxygen storage material can be used one type or in combination of two or more of these known oxygen storage materials.

Oxygen storage materials are generally in powder form. The particle shape of the powder is not particularly limited. Additionally, the average particle diameter is not particularly limited, but is preferably 5 μm or less, for example. If it is 5 μm or less, it is thought that a high oxygen storage capacity is exhibited due to the surface area. More preferably, it is 1㎛ or less. Moreover, it is more preferably 500 nm or less, more preferably 100 nm or less, even more preferably 50 nm or less, even more preferably 30 nm or less, and even more preferably 20 nm or less.

In addition, in this specification, when the average particle diameter of the oxygen storage material is less than 1 μm, the particle diameter is calculated after calculating the specific surface area by the BET method. In other words, the average particle diameter can be obtained from the specific surface area (㎡/g, S) obtained by analyzing the gas adsorption amount measured by the gas adsorption method using nitrogen (N ₂ ) gas as the adsorbent by the BET method (multi-point method or one-point method). there is. In addition, when measuring the amount of nitrogen gas adsorption, a sample degassed at 300°C under vacuum for more than 12 hours is subjected to gas adsorption at 77K. In addition, when the average particle diameter is 1 μm or more, it is calculated by the laser diffraction/scattering method that explains the average particle diameter of the layered compound.

The content of the oxygen storage material in the present composition is not particularly limited, and can be set to an effective amount that suppresses oxidation of the silsesquioxane derivative used. The oxygen storage material is, for example, 0.05% by mass or more, for example, 0.1% by mass or more, for example, 0.5% by mass or more, for example, 1% by mass, relative to the total mass of the silsesquioxane derivative and the oxygen storage material. or more, for example, 3% by mass or more, for example, 5% by mass or more, for example, 10% by mass or more, and for example, 15% by mass or more. In addition, with respect to the total amount of copper, it can be, for example, 25% by mass or less, and further, for example, 20% by mass or less. In addition, the content of the oxygen storage material can be, for example, 0.05 mass% or more and 50 mass% or less, 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 composition may include either or both a layered compound and an oxygen storage material. If both are included, each unique effect acts to effectively suppress the oxidation of the silsesquioxane derivative and achieve excellent heat resistance. Even in the case where both are contained, each may be contained within the content range already described. In addition, when the present composition includes both a layered compound and an oxygen storage material, the total mass of the layered compound and the oxygen storage material relative to the total mass of the silsesquioxane derivative, the layered compound, and the oxygen storage material is, for example, 10% by mass or more. It can be 80 mass% or less, for example, 15 mass% or more and 70 mass% or less, and for example, 20 mass% or more and 60 mass% or less.

(Aspects of this composition)

This composition can adopt various aspects. This composition contains, for example, an uncured (not crosslinked or polymerized by a polymerizable functional group) silsesquioxane derivative, and is a composition before film formation or molding (typically an irregular shape such as a liquid body). It can be.

The composition may also be, for example, a composition containing a cured product of a silsesquioxane derivative and formed in the form of a film or molded body formed on the surface of a workpiece.

(Composition containing uncured silsesquioxane derivative)

The composition of this embodiment may contain, for example, a silsesquioxane derivative having an organic functional group such as a polymerizable functional group, a layered compound, and/or an oxygen storage material. Additionally, if necessary, an initiator and/or a polymerization catalyst (curing agent) required for curing or polymerization may be included. The present composition includes a layered compound and/or an oxygen storage material along with an uncured silsesquioxane derivative, so that when the silsesquioxane derivative is exposed to heat, is cured by heating, or the cured product is exposed to heat. In such cases, heat resistance of the silsesquioxane derivative or its cured product is achieved. Additionally, a solvent may be included as another component.

(polymerization initiator)

The composition may include a polymerization initiator for polymerizing the silsesquioxane derivative with a polymerizable functional group. The type of polymerization initiator varies depending on the type of polymerizable functional group included in the silsesquioxane derivative, but various initiators and curing agents such as photoinitiators, thermal initiators, and radical polymerization initiators can be used. A person skilled in the art can appropriately select the type and usage amount of an appropriate polymerization initiator or curing agent, taking into consideration the polymerizable functional group to be used and the intended use of the composition. For example, known organic peroxides, azo compounds, etc. can be used as radical polymerization initiators.

Examples of organic peroxides include benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, paramenthan hydroperoxide, and di-t-butyl peroxide. Additionally, examples of azo compounds include azobisisobutyronitrile, azobisisovaleronitrile, and azobisisocapronitrile.

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 entire composition.

(hydrosilylation catalyst)

When the polymerizable functional group has an unsaturated organic group in the presence of a hydrosilyl group hydrogen atom, examples of the hydrosilylation catalyst used for curing (hydrosilylation) of the silsesquioxane derivative by hydrosilylation include cobalt, Examples include simple substances, organic metal complexes, metal salts, and metal oxides of metals of the 8th to 10th genera such as nickel, ruthenium, rhodium, palladium, iridium, and platinum. Usually, platinum-based catalysts are used. Platinum-based catalysts include cis-PtCl ₂ (PhCN) ₂ , platinum carbon, platinum complex coordinated with 1,3-divinyltetramethyldisiloxane (Pt(dvs)), platinum vinylmethyl cyclic siloxane complex, and platinum carbonyl/vinyl. Methyl cyclic siloxane complex, tris(dibenzylideneacetone) diplatinum, chloroplatinic acid, bis(ethylene)tetrachloro diplatinum, cyclooctadienechloroplatinum, bis(cyclooctadiene)platinum, bis(dimethylphenylphosphine)dichloroplatinum , tetrakis (triphenylphosphine) platinum, etc. are exemplified. Among these, 1,3-divinyltetramethyldisiloxane-coordinated platinum complex (Pt(dvs)), platinum vinylmethyl cyclic siloxane complex, and platinum carbonyl·vinylmethyl cyclic siloxane complex are particularly preferred. Additionally, Ph represents a phenyl group. The amount of catalyst used is preferably 0.1 ppm by mass to 1000 ppm by mass, more preferably 0.5 to 100 ppm by mass, and still more preferably 1 to 50 ppm by mass, relative to the amount of silsesquioxane derivative.

When this composition contains a catalyst for hydrosilylation reaction, the hydrosilylation reaction may take precedence over the dehydration polycondensation of the remaining alkoxy group or hydroxyl group in structural unit (1-5), and the hydrosilylation structural portion may be In some cases, it has the alkoxy group or hydroxyl group to enable further crosslinking reaction.

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

This composition may be a composition for use in film formation but may not substantially contain a hydrosilylation catalyst. As will be described later, silsesquioxane derivatives can be cured by promoting the hydrosilylation reaction through heat treatment even in the absence of a hydrosilylation catalyst. In the present composition, the fact that the hydrosilylation catalyst is substantially not contained means that, except in the case where the hydrosilylation catalyst is not intentionally added, the content of the hydrosilylation catalyst relative to the amount of the silsesquioxane derivative is, for example, 0.1. It is less than mass ppm, for example, 0.05 mass ppm or less.

(solvent)

The silsesquioxane derivative can be used as is, but if necessary, it can also be diluted with a solvent and used for film formation. The solvent is preferably one that dissolves the silsesquioxane derivative, and examples include aromatic hydrocarbon solvents, chlorinated hydrocarbon solvents, alcohol solvents, ether solvents, amide solvents, ketone solvents, ester solvents, cellosolve solvents, aliphatic hydrocarbon solvents, etc. Various organic solvents can be mentioned. Additionally, a solvent other than alcohol is preferable to avoid decomposition of Si-H groups in the presence of a hydrosilylation catalyst such as Pt.

(Other ingredients)

When this composition is provided for curing, various additives may be further added. Additives include, for example, reactive diluents such as tetraalkoxysilanes and trialkoxysilanes (trialkoxysilane, trialkoxyvinylsilane, etc.), and polymerizable functional groups of the same type or similar to the polymerizable functional groups provided by silsesquioxane derivatives. Monomers, oligomers, etc. having . These additives are used to the extent that they do not impair the heat resistance of the resulting cured product of the silsesquioxane derivative.

This composition can be formed into a film by supplying it to the surface of a workpiece having an arbitrary shape and curing it to form a film with excellent heat resistance. For example, the composition can be supplied to the surface of the area to be processed and then cured.

The supply of this composition to the surface of the workpiece is not particularly limited, but normal application methods such as spray coating, casting, spin coating, and bar coating can be used.

(Composition containing a cured product of silsesquioxane derivative)

The present composition may be a composition containing a cured product obtained by polymerizing a silsesquioxane derivative having a polymerizable functional group with a polymerizable functional group. These compositions may also contain layered compounds and/or oxygen storage materials. This composition is obtained, for example, 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.

As a cured product of the silsesquioxane derivative, the unreacted alkoxy group in the silsesquioxane derivative, that is, the alkoxy group or hydroxyl group of R ⁴ in the structural unit (1-5), is sufficiently formed to form a siloxane bond by dehydration and polycondensation. Examples include a cured product obtained by forming the cured product and curing it by further promoting crosslinking (curing by polycondensation of such remaining alkoxy groups, etc. is also called primary curing). This cured product (hereinafter also referred to as primary cured product) may be included in the silsesquioxane derivative represented by composition formula (1).

Other cured products of silsesquioxane derivatives are cured by promoting crosslinking through a reaction with the polymerizable functional groups included in structural units (1-2) to (1-4) (such curing is also called secondary curing). Can lift cargo. This cured product (hereinafter also referred to as secondary cured product) has a structure in which at least a portion of the polymerizable functional groups in the structural units of the silsesquioxane derivative are polymerized based on the inherent polymerizability of the functional group. It may include derivatives of silsesquioxane derivatives having moieties.

Other cured products of silsesquioxane derivatives are cured (such as Examples include hardened products in which curing is also referred to as secondary curing. This cured product (hereinafter also referred to as secondary cured product) is a silsesquioxane derivative in which at least some of the functional groups (hydrosilylation group and unsaturated organic group) that undergo hydrosilylation reaction in the structural units thereof are hydrosilyl group. A structural part (-Si-C-C-Rm-Si-, -Si-C=C-Rm-Si-) containing a carbon-carbon bond (single bond or double bond) derived from an unsaturated organic group formed through a chemical reaction (-Si-C-C-Rm-Si-) ( In this specification, it is also referred to as a hydrosilylated structural moiety. R is, for example, an organic group with 1 to 8 carbon atoms, and m is an integer of 0 or 1. It includes derivatives of silsesquioxane derivatives. can do.

When the composition adopts a film-forming form, the composition is generally a secondary cured product of a silsesquioxane derivative. In addition to the polymerization portion due to the polymerizable functional group, the hydrosilylated structural portion can contribute to practical membrane strength and membrane performance.

Primary curing of silsesquioxane derivatives sometimes follows secondary curing, and secondary curing sometimes follows primary curing, but secondary curing follows primary curing in many cases. Therefore, the cured product of the silsesquioxane derivative is generally a secondary cured product, and in many cases follows primary curing. A typical cured product is characterized by the presence or absence of a cross-linked structure due to secondary curing. The cured product can be detected by regularity (irregularity) of the structural units and structures such as Q unit, T unit, D unit, M unit, alkoxy group, etc. using ¹ H NMR, ²⁹ Si NMR, and IR spectrum. The composition or structure can be specified by detecting the characteristic group.

In addition to containing only the silsesquioxane derivative or its cured product, the composition may contain other components as needed.

(Oxidation inhibition method and heat resistance method)

The method for inhibiting oxidation of the silsesquioxane derivative or its cured product disclosed herein may include a step of heating the silsesquioxane derivative or its cured product together with a layered compound and/or an oxygen storage material. The method of suppressing oxidation is also a method of heat resistance of the silsesquioxane derivative or its cured product. In various embodiments of the present composition described above, in the process of producing the cured silsesquioxane derivative and the process of heating the cured product, oxidation of the silsesquioxane derivative or the cured product is carried out by the layered compound and/or the oxygen storage material. is suppressed. Therefore, by providing this process, oxidation of the silsesquioxane derivative or its cured product is suppressed and heat resistance is achieved.

In view of the above, according to the present specification, an oxidation inhibitor or heat resistance improver of a silsesquioxane derivative or a cured product thereof containing a layered compound and/or an oxygen storage material as an active ingredient is provided.

Example

Hereinafter, the present invention will be specifically explained by examples. However, the present invention is not limited to this example in any way. Additionally, the viscosity of the obtained silsesquioxane derivative was measured at 25°C using an E-type viscometer.

In addition, in the following description, parts and % all represent parts by mass and % by mass.

Example 1

(Preparation of composition containing silsesquioxane derivative and its cured product)

70 parts of a silsesquioxane derivative having a methacryloyl group in the T unit (manufactured by TOAGOSEI Co., Ltd., MAC-SQ TM-100, viscosity 4000 mPa·s), and talc (Nippon Talc Co., Ltd., SG95) , D50 = 2.5㎛) and 0.7 parts of thermal radical initiator (NOF CORPORATION, PERBUTYL E, t-butylperoxy-2-ethylhexyl monocarbonate) were weighed into a vial and stirred at 1800 rpm for 1 minute using a rotating mixer. By mixing, the composition of Test Example 1 was obtained.

The composition of Test Example 1 was applied to a sandblasted aluminum plate, bonded to the similarly sandblasted aluminum plate, heated at 120°C for 1 hour (DK63, manufactured by Yamato Scientific Co., Ltd.), and then heated at 150°C for an additional hour. The test piece of Test Example 1 was obtained by heating and thermal curing.

The test pieces were maintained in air at 350°C for 1 hour, 24 hours in air, and 24 hours in nitrogen atmosphere at 350°C, and the tensile shear strength of the test pieces was measured before temperature treatment and after cooling to room temperature.

The tensile shear strength of the test piece was measured using Strograph 20-C manufactured by TOYO SEIKI Co., Ltd. In addition, the tensile shear of the test piece while heated at 200°C was also measured. All tensile speeds were set at 10 millimeters/min. The results are shown in Table 1.

Additionally, as a control, a composition was prepared in the same manner as Test Example 1 using only the silsesquioxane derivative, and a test piece was prepared to be the test piece of Comparative Example A. Additionally, a composition containing bisphenol A type epoxy resin:talc (75 parts:25 parts) was prepared, and the composition was cured at 120°C for 1 hour and then at 150°C for 1 hour to obtain a test piece of Comparative Example B. The same temperature treatment was performed on the test pieces of Comparative Examples 1 and 2, and the tensile shear strength was measured for the test pieces before and after treatment. All results are shown in Table 1.

As shown in Table 1, the test specimen prepared from a talc-containing silsesquioxane derivative (Test Example 1) showed a decrease in tensile shear strength regardless of heating within 1 to several hours at 350°C in air, That is, the decline in adhesive strength was excellent and suppressed. In contrast, test specimens prepared with a silsesquioxane derivative without added talc (Comparative Example A) and a mixed composition of epoxy resin and talc (Comparative Example B) showed a significant decrease in tensile shear strength.

Example 2

(Thermal behavior of compositions containing silsesquioxane derivatives)

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

Mix 70 parts of the same silsesquioxane derivative (MAC-SQ TM-100) as used in Example 1 and 30 parts of talc (Nippon Talc Co., Ltd., three types of D50 = 1㎛, 2.5㎛, and 5㎛). Three types of curable compositions (liquid) were prepared.

(Preparation of silsesquioxane derivative (cured product) composition)

70 parts of silsesquioxane derivative (MAC-SQ TM-100), 30 parts of talc (SG25, Nippon Talc Co., Ltd., D50=2.5㎛), and 0.7 parts of thermal radical initiator (NOF CORPORATION, PERBUTYL E) Thermosetting composition A was prepared in the same manner as in Example 1, applied to a sandblasted aluminum plate, heated at 120°C for 1 hour (DK63, manufactured by Yamato Scientific Co., Ltd.), and then heated at 150°C for an additional hour. , heat curing was performed to obtain cured product A.

In addition, the same silsesquioxane derivative, talc (SG95), and ceria zirconia composite oxide (average particle diameter 5-10 nm) were mixed at a mass ratio of 7:3:1, respectively, and a thermal radical initiator (NOF CORPORATION, PERBUTYL E) ) 0.7 part was mixed, the thermosetting composition B was prepared in the same manner as in Example 1, and heat cured in the same manner as the thermosetting composition B to obtain the cured product B.

Additionally, the same silsesquioxane derivative and 0.7 parts of a thermal radical initiator (NOF CORPORATION, PERBUTYL E) were used in the same manner as in Example 1 to prepare a control thermosetting composition, which was applied to a sandblasted aluminum plate and incubated at 120°C. After heating for a time (DK63, manufactured by Yamato Scientific Co., Ltd.), it was further heated at 150°C for 1 hour and heat cured to obtain a control cured product.

(Evaluation of thermal behavior)

The three liquid compositions MAC-SQ TM-1 million and their thermal behavior were evaluated by TGA. The results are shown in Figure 1. Compositions were prepared, and the thermal behavior of these compositions was evaluated by TGA. In addition, the thermal behavior of the cured product of bisphenol A type epoxy resin was also evaluated. The results are shown in Figure 1. In addition, in Figure 1, in addition to the actual measured mass change (%) of various compositions, the effective weight change rate of the silsesquioxane derivative is calculated by multiplying the mass reduction of the talc-free silsesquioxane derivative by 0.7. The matched mass change was also described.

The thermal behavior of cures A, B and the control cure was evaluated by TGA. The results are shown in Figure 2. Figure 2(a) shows the weight change rate from 0°C to 1000°C, and (b) shows the weight change rate over an expanded temperature range from 300°C to 600°C.

As shown in FIG. 1, by addition of talc, the weight loss start temperature indicating oxidation of the silsesquioxane derivative-containing composition (liquid, uncured curable composition) shifts to the high temperature side, and the polymerization decrease temperature is lower than that of bisphenol A type epoxy. It was found that the temperature shifted to the higher temperature side by more than 20℃ compared to the resin. In addition, the average particle size of talc was 1 to 5 μm, resulting in a shift in the weight loss temperature toward higher temperatures. Additionally, when TGA was performed on these compositions in nitrogen, there was no difference in the presence or absence of talc.

In addition, as shown in Figure 2, it was found that the polymerization reduction start temperature, which indicates oxidation, shifted to the high temperature side for the silsesquioxane derivative cured product.

From the above, it was found that the improvement in heat resistance by layered compounds such as talc and/or oxygen storage materials was caused by suppression of oxidation of the silsesquioxane derivative (uncured) and its cured product. Additionally, it was found that oxidation was further suppressed by adding 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 materials)

The composition and test piece of Test Example 1 were prepared in the same manner as Example 1. In addition, the compositions of Test Examples 1 to 17 were prepared in the same manner as in Test Example 1 of Example 1, except that each part of the components shown in the table below were used, and each test piece was prepared.

(Comparative Examples 1 to 3 of cured products containing only silsesquioxane derivatives or silsesquioxane derivatives and other components)

The composition of Comparative Example 1 was prepared in the same manner as Example 1, and the same operation as for Test Example 1 of Example 1 was performed except that the test pieces were prepared and the components shown in the table below were used, and Comparative Examples 2 and 3 were obtained. The composition and test piece were prepared.

(Comparative Examples 4 to 5 of cured epoxy resin)

The same operation as for Comparative Example 2 in Example 1 was performed to prepare the compositions and test pieces of Comparative Examples 4 and 5.

Some of these test pieces were heated at 350°C for 1 hour. Additionally, some test pieces were heated at 200°C for 95 hours, 430 hours, and 1000 hours. All were heated using DK63 manufactured by Yamato Scientific Co., Ltd. in the same manner as in Example 1. In addition, some test pieces were heated at 250°C for 95 hours, 430 hours, and 1000 hours.

A tensile shear strength test was performed on the test pieces before and after temperature treatment according to Example 1. In addition, a tensile shear test while heating at 200°C was also performed on some of the test specimens. The results are shown in Table 2.

In addition, the notations in the table are explained below.

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

AC-SQ TA-100: Radical curable silsesquioxane derivative containing an acryloyl group (manufactured by TOAGOSEI Co., Ltd.)

Epoxy resin: Bisphenol A type epoxy resin

Talc SG95: Talc (layered magnesium silicate compound), D50 = 2.5 μm (manufactured by Nippon Talc Co., Ltd.)

Talc SG2000: Talc (layered magnesium silicate compound), D50=1㎛ (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 2-3 ㎛ (manufactured by Wako Pure Chemical Industries, Ltd.)

Ceria zirconia composite oxide: CeO ₂ /ZrO ₂ , average particle diameter 5 to 10 nm

Ceria 1: CeO ₂ , average particle diameter 5∼10 nm

Ceria 2: CeO ₂ , average particle diameter 5.5㎛

Zirconia: ZrO ₂ , average particle diameter 10 to 15 nm

Ferric oxide: Fe ₂ O ₃ , average particle diameter 50 nm or less

PERBUTYL E: t-butylperoxy-2-ethylhexyl monocarbonate (manufactured by NOF CORPORATION)

Additionally, the D50 of talc was performed using a dispersion liquid in which talc was dispersed using ultrasonic waves, using SALD200 (manufactured by Shimadzu Corporation). A particle size distribution measuring device based on a commercially available laser diffraction/scattering method can be used. In addition, the average particle diameter of hexagonal boron nitride was set to D50, which was measured based on the particle size distribution obtained by laser diffraction/scattering method.

The average particle size of ceria zirconia composite oxide, ceria 1, zirconia, and ferric oxide is the ratio obtained by analyzing the gas adsorption amount measured by the gas adsorption method using nitrogen (N ₂ ) gas as the adsorbent by the BET method (multipoint method). The average particle diameter was determined from the surface area (m2/g, S). In addition, in measuring the amount of nitrogen gas adsorption, each sample was degassed at 300°C under vacuum for more than 12 hours, and then gas was adsorbed at 77K. Additionally, Ceria 2 was measured using a laser diffraction/scattering method like talc based on the particle diameter relationship.

As shown in Table 2, test specimens bonded with a cured silsesquioxane derivative cured containing only a layered compound (Test Examples 1 to 5), test specimens bonded with a cured derivative cured containing a layered compound and an oxygen storage material (Test Examples 6 to 16) and test specimens (Test Example 17) bonded with a cured derivative cured containing only an oxygen storage material, the decline in tensile shear strength was excellent and suppressed before and after temperature treatment. Among them, the rate of change in tensile shear strength after heat treatment at 350°C for 1 hour in Test Examples 1 to 17, Comparative Example 1 of only the silsesquioxane derivative cured product, and the silsesquioxane derivative cured product containing other components. In comparison with the change rates of Comparative Examples 2 to 3 and Comparative Example 4 using an epoxy resin, the decrease in tensile shear strength at 350°C was well suppressed in the test specimens using the layered compound and/or oxygen storage material. Could know. Additionally, even if silica, calcium carbonate, etc. were added, it was the same as not adding anything at all. In addition, as a result of obtaining cured products of mica and smectite, which are minerals that are a type of layered compound, in the same manner as in Test Example 1, and measuring the adhesive strength in the same manner, it was also confirmed that the effect of adding the layered compound could be obtained.

In addition, according to Test Examples 6 to 16 containing both the layered compound and the oxygen storage material, containing both of these is effective in suppressing the decrease in tensile shear strength after heat treatment (heat resistance), and they act synergistically. could know that In addition, it was found that a high heat resistance effect was obtained even at 350°C for 1 hour and when held for a long time at 200°C or 250°C. In addition, it was found that even when the polymerizable functional group was a methacryloyl group, an almost equivalent heat resistance effect was obtained compared to a silsesquioxane derivative having an acryloyl group.

Additionally, regarding the layered compound, as shown in Test Examples 1 to 5, a sufficient effect is obtained by using 3 parts to 7 parts of the silsesquioxane derivative, so the total mass of the silsesquioxane derivative and the layered compound For example, it was found that the heat resistance effect is exhibited in a range of 5% to 50%, preferably 10% to 40%, more preferably 20% to 40%. Additionally, regarding the oxygen storage material, as shown in Test Examples 6 to 17, the oxygen storage material is effective if it is, for example, 0.007% or more, with respect to the total mass of the silsesquioxane derivative and the oxygen storage material, and is more effective if it is 0.4% or more. And, it was found that it was more effective if it was 10% or more, and it was also more effective if it was 20% or more. In addition, sufficient adhesive strength was shown even when the addition amount was 30%. From the above points, it can be seen that the oxygen storage material can be, for example, 0.07% or more and 30% or less, preferably 0.4% or more and 20% or less, relative to the total mass of the silsesquioxane derivative and the oxygen storage material. In addition, when the layered compound and the oxygen storage material were included, it was found that sufficient adhesive strength could be maintained even if the content exceeded 40% of the total mass of the silsesquioxane derivative, the layered compound, and the oxygen storage material.

In addition, the oxygen storage material showed a heat resistance effect for the cured silsesquioxane derivative, but did not sufficiently exhibit a heat resistance effect for the epoxy resin.

From the above points, it was found that the action of the layered compound and the oxygen storage material acts more effectively on the silsesquioxane derivative or its cured product.

In addition, both talc and hexagonal boron nitride, which are layered compounds, exhibited excellent heat resistance, but it was found that the heat resistance was greater when the average particle diameter was small. That is, when the average particle diameter exceeded 5 μm, the heat resistance effect tended to be irregular. Accordingly, it was found that the average particle diameter of the layered compound is less than 5 μm, preferably 4 μm or less, and more preferably 3 μm or less.

In addition, it was found that the oxygen storage materials of Examples 1 to 5 and Comparative Example 1 exhibited a higher heat resistance effect. Among the oxygen storage materials, it was found that ceria zirconia composite oxide, which has a high oxygen storage capacity, also had the highest oxidation resistance. Also, in the case of the oxygen storage material, if the average particle diameter exceeds 5 μm, the oxidation resistance tends to decrease, and the average particle diameter of the oxygen storage material is preferably less than 5 μm, more preferably 4 μm or less, and further. It was found that it is preferably 3 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.

Example 4

(Thermal behavior of other silsesquioxane derivative cured compositions)

A silsesquioxane derivative having an oxetanyl group shown below in _1.5 SiO units (OX-SQ, TX-100, manufactured by TOAGOSEI Co., Ltd., hereinafter referred to as silsesquioxane A) ) and similarly, a silsesquioxane derivative (TOAGOSEI Co., Ltd., hereinafter referred to as silsesquioxane B) having _1.5 SiO units of an epoxy group shown below is used, and talc (SG95) and ceria zirconia composite oxide are used. (average particle diameter: 5 to 10 nm) were used and mixed at a mass ratio of 7:3:1 to prepare a composition (liquid phase), and the thermal behavior of these compositions was evaluated by TGA. In addition, TGA was similarly performed only for silsesquioxane A and B. The results are shown in Figure 3. In addition, in Figure 3, based on the actual measured mass change (%) for silsesquioxane A and B, the mass change was multiplied by 0.63 to cancel out the presence of talc, etc. in the composition. The respective mass changes of A and B are shown.

As shown in Figure 3, it was found that the weight loss onset temperature, which indicates oxidation of curing of the silsesquioxane derivative, shifted to the high temperature side by the addition of talc and ceria zirconia composite oxide.

From the above points, it was found that the layered compound and the oxygen storage material similarly exert oxidation inhibition and heat resistance effects on the silsesquioxane cured product having such a polymerizable functional group.

Claims (17)

A silsesquioxane derivative represented by the following formula (1),
Layered compounds,
Contains an oxygen storage material,
The oxygen storage material is one or two or more types selected from the group consisting of ceria, zirconia, and ceria-zirconia composite oxide,
A curable silsesquioxane derivative composition, wherein the silsesquioxane derivative is cured by polymerization and/or crosslinking by at least the polymerizable functional group of the silsesquioxane derivative represented by the formula (1).

(In equation (1), w and x are positive numbers, v, y and z are 0 or positive numbers,
R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group,
R ² each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group. ,
R ³ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group. ,
R ⁴ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
At least one of R ¹ , two R ² and three R ³ represents a polymerizable functional group.
However, this excludes cases where all polymerizable functional groups are vinyl groups.) According to claim 1,
A composition wherein the layered compound is one or two or more selected from the group consisting of talc and boron nitride. The method of claim 1 or 2,
A composition wherein the layered compound is talc. The method of claim 1 or 2,
A composition wherein the average particle diameter of the layered compound is 5㎛ or less. The method of claim 1 or 2,
A composition containing the layered compound in an amount of 5% by mass or more and 50% by mass or less based on the total mass of the silsesquioxane derivative and the layered compound. The method of claim 1 or 2,
A composition in which the oxygen storage material is ceria zirconia composite oxide. The method of claim 1 or 2,
A composition containing the oxygen storage material in an amount of 0.1% by mass or more and 40% by mass or less based on the total mass of the silsesquioxane derivative and the oxygen storage material. The method of claim 1 or 2,
A composition wherein the polymerizable functional group includes a (meth)acryloyl group, an oxetanyl group, or an epoxy group. The method of claim 1 or 2,
A composition for forming a heat-resistant film. A silsesquioxane derivative represented by the following formula (1) is a cured product obtained by curing the silsesquioxane derivative through at least polymerization and/or crosslinking with a polymerizable functional group,
Layered compounds,
Contains an oxygen storage material,
The silsesquioxane derivative cured composition, wherein the oxygen storage material is one or two or more selected from the group consisting of ceria, zirconia, and ceria-zirconia composite oxide.

(In equation (1), w and x are positive numbers, v, y and z are 0 or positive numbers,
R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group,
R ² each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group. ,
R ³ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group. ,
R ⁴ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
At least one of R ¹ , two R ² and three R ³ represents a polymerizable functional group.
However, this excludes cases where all polymerizable functional groups are vinyl groups.) A process of heating a silsesquioxane derivative represented by the following formula (1), a layered compound, and an oxygen storage material is provided,
A method of inhibiting oxidation of a silsesquioxane derivative or a cured product thereof, wherein the oxygen storage material is one or two or more selected from the group consisting of ceria, zirconia, and ceria-zirconia composite oxide.

(In equation (1), w and x are positive numbers, v, y and z are 0 or positive numbers,
R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group,
R ² each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group. ,
R ³ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group. ,
R ⁴ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
At least one of R ¹ , two R ² and three R ³ represents a polymerizable functional group.
However, this excludes cases where all polymerizable functional groups are vinyl groups.) A process of heating a silsesquioxane derivative represented by the following formula (1), a layered compound, and an oxygen storage material is provided,
A method for heat resistance of a silsesquioxane derivative or a cured product thereof, wherein the oxygen storage material is one or two or more selected from the group consisting of ceria, zirconia, and ceria-zirconia composite oxide.

(In equation (1), w and x are positive numbers, v, y and z are 0 or positive numbers,
R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group,
R ² each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group. ,
R ³ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group. ,
R ⁴ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
At least one of R ¹ , two R ² and three R ³ represents a polymerizable functional group.
However, this excludes cases where all polymerizable functional groups are vinyl groups.) It contains layered compounds and oxygen storage materials as active ingredients,
An oxidation inhibitor of a silsesquioxane derivative or a cured product thereof represented by the following formula (1), wherein the oxygen storage material is one or two or more selected from the group consisting of ceria, zirconia, and ceria-zirconia composite oxide.

(In equation (1), w and x are positive numbers, v, y and z are 0 or positive numbers,
R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group,
R ² each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group. ,
R ³ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group. ,
R ⁴ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
At least one of R ¹ , two R ² and three R ³ represents a polymerizable functional group.
However, this excludes cases where all polymerizable functional groups are vinyl groups.) It contains layered compounds and oxygen storage materials as active ingredients,
A heat resistance improver of a silsesquioxane derivative or a cured product thereof represented by the following formula (1), wherein the oxygen storage material is one or two or more selected from the group consisting of ceria, zirconia, and ceria-zirconia composite oxide.

(In equation (1), w and x are positive numbers, v, y and z are 0 or positive numbers,
R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group,
R ² each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group. ,
R ³ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or a polymerizable functional group. ,
R ⁴ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
At least one of R ¹ , two R ² and three R ³ represents a polymerizable functional group.
However, this excludes cases where all polymerizable functional groups are vinyl groups.) delete delete delete