JP7276348B2 - Silsesquioxane derivative composition and use thereof - Google Patents

Description

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

(Cross reference to related applications)
This application is a related application of Japanese Patent Application No. 2018-196951, which is a Japanese patent application filed on October 18, 2018, and claims priority based on this Japanese application. shall incorporate all content provided herein.

Silsesquioxane is a compound having a three-dimensional crosslinked structure formed by siloxane bonds and having a unit represented by RSiO _1.5 as a structural unit, and R may include various functional groups including organic functional groups. can. Such silsesquioxane derivatives (silsesquioxane derivatives) are known as excellent heat-resistant materials (Patent Documents 1 and 2). In addition, since the silsesquioxane derivative is an inorganic-organic hybrid material, it can exhibit organic properties such as flexibility and solubility in addition to inorganic properties such as heat resistance. For example, certain silsesquioxane derivatives have polymerizable functional groups such as epoxy groups as organic groups, and are therefore used as curable adhesives (Patent Document 3).

WO2005/10077 WO2009/66608 JP 2018-95819 A

According to the present inventors, depending on the conditions such as the atmosphere and heating temperature, the organic group provided in the silsesquioxane derivative is oxidized, resulting in, for example, deterioration of the original mechanical properties at high temperatures. It has been found that the properties of silsesquioxanes can vary.

However, no technology has been reported for suppressing the oxidation of organic groups in silsesquioxane. Moreover, since silsesquioxane is known to have high heat resistance, no effective technique for further improving its heat resistance has been provided. Furthermore, the current situation is that no study has been made on a technique for ensuring heat resistance under such severe conditions that the organic groups in the silsesquioxane are oxidized.

The present specification provides a technique for enhancing heat resistance by suppressing oxidation of silsesquioxane and its use.

The present inventors focused on the possibility of the presence of an additive capable of suppressing the oxidation of the organic group in the silsesquioxane derivative, and 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, can improve the heat resistance of the silsesquioxane derivative. This specification provides the following means based on these findings.

[1] a silsesquioxane derivative;
a layered compound;
A silsesquioxane derivative composition containing
[2] The composition according to [1], wherein the layered compound is one or more 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 size of 5 μm or less.
[5] The layered compound material according to any one of [1] to [4], containing 5% by mass or more and 50% by mass or less of the total mass of the silsesquioxane derivative and the layered compound. Composition.
[6] The composition according to any one of [1] to [5], further containing an oxygen storage material.
[7] a silsesquioxane derivative;
an oxygen storage material;
A silsesquioxane derivative composition containing
[8] The composition according to [6] or [7], wherein the oxygen storage material is one or more selected from the group consisting of ceria, zirconia and ceria-zirconia composite oxides.
[9] The composition according to any one of [6] to [8], wherein the oxygen storage material is a ceria-zirconia composite oxide.
[10] Any one of [6] to [9], containing 0.1% by mass or more and 40% by mass or less of the oxygen storage material with respect to the total mass of the silsesquioxane derivative and the oxygen storage material. The composition according to .
[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 layered compound and/or an oxygen storage material;
A curable silsesquioxane derivative composition comprising:
[13] A cured product of a silsesquioxane derivative having a polymerizable functional group;
a layered compound and/or an oxygen storage material;
A silsesquioxane derivative cured product composition.
[14] A method for suppressing oxidation of a silsesquioxane derivative or a cured product thereof, comprising the step of heating the silsesquioxane derivative together with a layered compound and/or an oxygen storage material.
[15] a step of heating a silsesquioxane derivative together with a layered compound and/or an oxygen storage material;
A method for increasing heat resistance of a silsesquioxane derivative or a cured product thereof.
[16] An oxidation inhibitor for 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 for a silsesquioxane derivative or a cured product thereof containing a layered compound and/or an oxygen storage material as an active ingredient.

FIG. 2 shows the thermal behavior of silsesquioxane derivatives with methacryloyl groups. FIG. 2 is a diagram showing thermal behavior of a cured product of a silsesquioxane derivative; FIG. 4 shows the thermal behavior of other silsesquioxane derivatives with oxetanyl and epoxy groups.

The disclosure of the present specification 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 specification, the presence of the layered compound suppresses the oxidation of the silsesquioxane derivative, thereby improving the stability of the silsesquioxane derivative, particularly the stability to heat (heat resistance). can be made It is not always clear why layered compounds produce such effects. It is considered that the gas barrier property and gas diffusion suppression property of the layered compound are involved in the suppression of oxidation of the organic groups.

The disclosure of the present specification also shows that the presence of an oxygen storage material suppresses oxidation of the silsesquioxane derivative, and thus improves the stability of the silsesquioxane derivative, particularly the stability to heat (heat resistance). can be improved. Such an action is considered to be due to the oxidation/reduction of itself by the oxygen storage material, the adsorption of oxygen, and the like.

The silsesquioxane derivatives can have various organic groups, for example, polymerizable functional groups. When such silsesquioxane derivatives are polymerized, decomposition due to oxidation of these polymerizable functional groups may greatly affect the properties of the silsesquioxane derivatives. Therefore, it is significant to impart oxidation resistance to a silsesquioxane derivative composition containing a silsesquioxane derivative having such a functional group and to a cured product obtained from the composition with a layered compound and/or an oxygen storage material. is.

Hereinafter, representative and non-limiting specific examples of the present disclosure will be described in detail with reference to the drawings as appropriate. This detailed description is merely intended to present those skilled in the art with details for implementing preferred embodiments of the disclosure, and is not intended to limit the scope of the disclosure. In addition, the additional features and inventions disclosed below may be used separately or together with other features and inventions to provide further improved "silsesquioxane derivative compositions and uses thereof." can be done.

Also, any combination of features and steps disclosed in the following detailed description are not required to practice the disclosure in its broadest sense, but are specifically intended to illustrate exemplary embodiments of the disclosure. is described. Moreover, various features of the representative embodiments above and below, as well as those set forth in the independent and dependent claims, are described herein in providing additional and useful embodiments of the present disclosure. They do not have to be combined in the exact order given or in the order listed.

All features set forth in the specification and/or claims, apart from the configuration of the features set forth in the examples and/or claims, are hereby incorporated by reference as limitations on the particular matter claimed in the original disclosure, and individually: and are intended to be disclosed independently of each other. Moreover, all numerical ranges and groupings or populations are intended to disclose configurations intermediate therebetween as limitations on the original disclosure as well as the specific subject matter claimed.

Various embodiments of the technology for suppressing oxidation of the silsesquioxane derivative according to the present disclosure and its utilization will be described below. Specifically, regarding a silsesquioxane derivative composition, a silsesquioxane derivative cured product composition, a method for suppressing oxidation or improving heat resistance of silsesquioxane, an oxidation inhibitor for silsesquioxane or a heat resistance improver, etc. explain.

(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, a layered compound and/or an oxygen storage material. .

(Silsesquioxane derivative)
As used herein, silsesquioxane is a polysiloxane whose main chain skeleton is composed of Si--O bonds and which is composed of (RSiO _1.5 ) units. In the present specification, the silsesquioxane derivative is a compound having one or more units represented by such polysiloxane and (RSiO _1.5 ) (T unit).

Silsesquioxane derivatives are represented, for example, by the following formula (1) comprising structural units (1-1), (1-2), (1-3), (1-4) and (1-5) be able to. v, w, x, y and z in formula (1) each represent the number of moles of structural units (1-1) to (1-5). In formula (1), v, w, x, y and z mean the average ratio of the number of moles of each structural unit contained in one molecule of the silsesquioxane derivative.

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

The silsesquioxane derivative has five structural units in formula (1), namely structural unit (1-1), structural unit (1-2), structural unit (1-3) and structural unit (1-4). Structural units selected from may be provided in combination so as to contain at least one polymerizable functional group.

In addition, the silsesquioxane derivative contains at least the structural unit (1-2). The silsesquioxane derivative can also contain the structural unit (1-3) together with the 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 only of the structural unit (1-2) (w is positive and the others are 0).

<Constituent unit (1-1): Q unit>
This structural unit remains as represented by formula (1) and defines the Q unit as a basic structural unit of polysiloxane. The number of this structural unit in the silsesquioxane derivative is not particularly limited.

<Constituent unit (1-2): T unit>
This structural unit defines the T unit as a basic structural unit of polysiloxane. R ¹ of this structural unit is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (hereinafter also referred to as a unit, C _1-10 alkyl group), an alkenyl group having 1 to 10 carbon atoms, It can be at least one selected from the group consisting of 1 to 10 alkynyl groups, aryl groups, aralkyl groups, and polymerizable functional groups.

R ¹ may be a hydrogen atom. In the case of a hydrogen atom, for example, the present structural unit and/or other structural units include an organic group having 2 to 10 carbon atoms containing a hydrosilylatable carbon-carbon unsaturated bond included in the polymerizable functional group ( Hereinafter, it may be simply referred to as an unsaturated organic group.), a cross-linking reaction can occur between these units.

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

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

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

R ¹ may be an aryl group. The number of carbon atoms is, for example, 6 or more and 20 or less, and is, for example, 6 or more and 10 or less. Aryl groups include phenyl, 1-naphthyl and 2-naphthyl groups.

R ¹ may be an aralkyl group. The number of carbon atoms is, for example, 7 or more and 20 or less, and is, for example, 7 or more and 10 or less. Aralkyl groups include phenylalkyl groups such as benzyl groups.

R ¹ may be a polymerizable functional group. The polymerizable functional group includes, for example, a thermosetting or photocurable polymerizable functional group. The polymerizable functional group is not particularly limited, and includes the above-mentioned functional groups such as vinyl group, allyl group, styryl group, methacryloyl group, acryloyl group, acryloyloxy group, methacryloyloxy group, α- Functionality with methylstyryl groups, vinyl ether groups, vinyl ester groups, acrylamide groups, methacrylamide groups, N-vinylamide groups, maleate groups, fumarate groups, N-substituted maleimide groups, isocyanate groups, oxetanyl groups and epoxy groups and the like. Among them, polymerizable functional groups having a (meth)acryloyl group, an oxetanyl group and an epoxy group are exemplified.

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. R ⁶ is preferably an alkylene group having 2 to 10 carbon atoms.

Examples of the oxetanyl group include, but are not limited to, (3-ethyl-3-oxetanyl)methyloxy group, (3-ethyl-3-oxetanyl)oxy group and the like. As the group containing an oxetanyl group, a group represented by the following formula or a group containing this group is preferable.

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. ^R7 is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably an ethyl group. R ⁸ is preferably an alkylene group having 2 to 6 carbon atoms, more preferably a propylene group.

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

The polymerizable functional group is the unsaturated organic group described above, that is, a functional group having a carbon-carbon double bond or a carbon-carbon triple bond capable of hydrosilylation reaction with a hydrogen atom (hydrosilyl group) bonded to a silicon atom. may be 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 groups and alkynyl groups described above. Examples include, but are not limited to, vinyl group, orthostyryl group, metastyryl group, parastyryl group, acryloyl group, methacryloyl group, acryloxy group, methacryloxy group, 1-propenyl group, 1-butenyl 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, phenylbutynyl group, allyl (2- propenyl) group, octenyl(7-octen-1-yl) group, and the like. Such unsaturated organic groups are, for example, vinyl groups, parastyryl groups, allyl (2-propenyl) groups, octenyl (7-octen-1-yl) groups and also, for example, vinyl groups.

In addition, two or more types of polymerizable functional groups can be contained in the entire silsesquioxane derivative, and in this case, all the polymerizable functional groups may be the same or different. In addition, the plurality of polymerizable functional groups may be the same, and may contain different polymerizable functional groups.

All of the C _1-10 alkyl group, C _1-10 alkenyl group, C _1-10 alkynyl group, aryl group, aralkyl group and polymerizable functional group may be substituted. Such substituents include halogen atoms such as fluorine, chlorine, bromine and chlorine atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t - Alkyl groups such as butyl group, 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), optionally substituted with at least one of a cyano group and a protected hydroxyl group.

The hydroxyl-protecting 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 protecting group represented by -C(=O)R (wherein R is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, an alkyl group having 1 to 6 carbon atoms such as isobutyl group, s-butyl group, t-butyl group, n-pentyl group; Substituents of the phenyl group having, 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, alkyl group such as isooctyl group; fluorine atom, chlorine atom, halogen atom such as bromine atom; methoxy group, alkoxy group such as ethoxy group, etc.), trimethylsilyl group, triethylsilyl group, Silyl protecting groups such as t-butyldimethylsilyl group and t-butyldiphenylsilyl group; methoxymethyl group, methoxyethoxymethyl group, 1-ethoxyethyl group, tetrahydropyran-2-yl group, tetrahydrofuran-2-yl group Acetal protecting groups such as; alkoxycarbonyl protecting groups such as t-butoxycarbonyl group; methyl group, ethyl group, t-butyl group, octyl group, allyl group, triphenylmethyl group, benzyl group, p-methoxy ether-based protective groups such as benzyl group, fluorenyl group, trityl group, benzhydryl group; and the like.

The silsesquioxane derivative can comprise one or a combination of two or more of these structural units. For example, R ¹ of one main structural unit can be an alkyl group, and R ¹ of another structural unit can be a polymerizable functional group. Further, for example, R ¹ of one main structural unit may be a hydrogen atom, and R ¹ of another 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. Although w is not particularly limited, for example, w/(v+w+x+y) is 0.25 or more, for example, 0.3 or more, or for example, 0.35 or more. 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, or for example 0.9 or more , also for example greater than or equal to 0.95, also for example greater than or equal to 0.99, also for example 1.

<Constituent unit (1-3): D unit>
This structural unit defines the D unit as a basic structural unit of the silsesquioxane derivative. R ² of this structural unit is at least selected from the group consisting of a hydrogen atom, a C _1-10 alkyl group, a C _1-10 alkenyl group, a C _1-10 alkynyl group, an aryl group, an aralkyl group and a polymerizable functional group. It can be one type. R ² in this structural unit may be the same or different.

Regarding the C _1-10 alkyl group, C _1-10 alkenyl group, C _1-10 alkynyl group, aryl group, aralkyl group, and polymerizable functional group, the various embodiments already described can be applied to this structural unit as they are.

The silsesquioxane derivative can comprise one or a combination of two or more of these structural units. In the silsesquioxane derivative, at least some of the structural units are C 1-10 alkyl groups, for example, both R ² are C _1-10 alkyl groups, and for example, all the structural ^units are Both are C _1-10 alkyl groups.

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

<Constituent unit (1-4): M unit>
This structural unit defines the M unit as a basic structural unit of the silsesquioxane derivative. R ³ of this structural unit is at least selected from the group consisting of a hydrogen atom, a C _1-10 alkyl group, a C _1-10 alkenyl group, a C _1-10 alkynyl group, an aryl group, an aralkyl group and a polymerizable functional group. It can be one type. It can be at least one selected from the group consisting of a hydrogen atom, a polymerizable functional group, and a _C1-10 alkyl group. Each R ³ in this structural unit may be the same or different.

Regarding the C _1-10 alkyl group, C _1-10 alkenyl group, C _1-10 alkynyl group, aryl group, aralkyl group, and polymerizable functional group, the various embodiments already described can be applied to this structural unit as they are.

The silsesquioxane derivative can comprise one or a combination of two or more of these structural units. In the silsesquioxane derivative, at least some of the structural units are C ^1-10 alkyl groups, for example, both R ³ are C _1-10 alkyl groups, and for example, all the structural units are Both are C _1-10 alkyl groups.

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. 0.4 or more. The numerical value is, for example, 0.5 or less, or for example, 0.45 or less.

<Constituent unit (1-5)>
This structural unit defines a unit containing an alkoxy group or a hydroxyl group in the 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 linear or branched. Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, butyl, pentyl and hexyl groups. Typical examples are alkyl groups having 2 to 10 carbon atoms such as methyl group, ethyl group, n-propyl group and isopropyl group, and also alkyl groups having 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 to be described later, or an alcohol contained in the reaction solvent substituted the hydrolyzable group of the raw material monomer. It is an "alkoxy group" that remains in the molecule without hydrolysis or polycondensation. In addition, the hydroxyl group in this structural unit is, for example, a hydroxyl group remaining in the molecule without polycondensation after the "alkoxy group" is hydrolyzed.

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

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

<Molecular weight etc.>
The number average molecular weight of the silsesquioxane derivative is preferably in the range of 300-10,000. Such a silsesquioxane derivative itself has a low viscosity, is easily dissolved in an organic solvent, the viscosity of the solution is easy to handle, and is excellent in storage stability. Considering coatability, storage stability, heat resistance, etc., 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, and preferably 500 to 2,000. The number-average molecular weight can be determined by GPC (gel permeation chromatography), for example, using polystyrene as a standard substance under the measurement conditions in [Examples] described later.

The silsesquioxane derivative is preferably liquid. When the silsesquioxane derivative is liquid, 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, from the viewpoint of filler mixing.

<Method for producing silsesquioxane derivative>
Silsesquioxane derivatives can be produced by known methods. Methods for producing silsesquioxane derivatives are disclosed in WO 2005/010077, WO 2009/066608, WO 2013/099909, JP 2011-052170 and JP 2013-147659. et al., are disclosed in detail as a method for producing polysiloxane.

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

In this specification, specifically, a Q monomer that forms the structural unit (1-1), a T monomer that forms the structural unit (1-2), and a D monomer that forms the structural unit (1-3) And, of the M monomers forming the structural unit (1-4), at least the T monomer is used. It is preferable to include a distillation step of distilling off the reaction solvent, by-products, residual monomers, water, etc. in the reaction solution after hydrolysis and polycondensation reaction of the raw material monomers in the presence of the reaction solvent.

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

In synthesizing the silsesquioxane derivative, a silicone compound having a siloxane bond-forming group represented by the following formulas (2) and (3) (hereinafter also referred to as a D oligomer) is used in place of the D monomer. can also

(In formulas (2) and (3) above, X is a siloxane bond forming group, R ⁹ and R ¹² are each an alkoxy group, an aryloxy group, an alkyl group, a cycloalkyl group, or an aryl group, and R ¹⁰ , R ¹¹ and R ¹³ are each an alkyl group, a cycloalkyl group or an aryl, and m and n are positive integers.)

The siloxane bond-forming group of the D oligomer means an atom or atomic group capable of forming a siloxane bond with the silicon atom in the silane compound, and specific examples thereof include methoxy, ethoxy, n-propoxy alkoxy groups such as i-propoxy group, n-butoxy group, i-butoxy group and t-butoxy group; cycloalkoxy groups such as cyclohexyloxy group; aryloxy groups such as phenyloxy group; be. The D oligomer represented by Formula 2 has two siloxane bond forming groups in one molecule, and these groups may be the same group or different groups.

As the D-oligomer, those in which the siloxane bond forming group is a hydroxyl group are readily available.

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

Each of R ¹⁰ , R ¹¹ and R ¹³ in the D oligomer is an alkyl group, a cycloalkyl group or an aryl group, and multiple R ¹⁰ and R ¹¹ present in one molecule may be the same group or different groups. may be a base. 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 and the like. be. As the D oligomer, those in which a plurality of R ¹⁰ and R ¹¹ present in one molecule are methyl groups or phenyl groups can be produced from inexpensive raw materials, and the cured product obtained using this composition is For example, it is preferable because it has excellent adhesiveness and the like, and it is particularly preferable that all the groups are methyl groups.

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

In the condensation step, the siloxane bond forming group of the Q monomer, T monomer or 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 an alkoxy group or a siloxy group. is preferred. Moreover, the monomers and oligomers corresponding to each structural unit may be used alone, or two or more of them may be used in combination.

Examples of the Q monomer that gives the structural unit (1-1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like. Examples of T monomers that give the structural unit (1-2) include trimethoxysilane, triethoxysilane, tripropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane. silane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, trichlorosilane and the like. Examples of T monomers that give 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-methacryloyloxypropyl)trimethoxysilane, (3-methacryloyloxypropyl)triethoxysilane, (3-acryloyloxypropyl)trimethoxy silane, (3-acryloyloxypropyl)triethoxysilane, and the like. Examples of the D monomer that gives the structural unit (1-3) include dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, diethoxydiethylsilane, dipropoxydimethylsilane, dipropoxydiethylsilane, dimethoxybenzylmethylsilane, diethoxybenzyl methylsilane, dichlorodimethylsilane, dimethoxymethylsilane, dimethoxymethylvinylsilane, diethoxymethylsilane, diethoxymethylvinylsilane and the like. The M monomer that gives the structural unit (1-4) includes hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, 1,1,3,3 that gives two structural units (1-4) by hydrolysis. -tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, methoxydimethylsilane, ethoxydimethylsilane, methoxydimethylvinylsilane, ethoxydimethylvinylsilane, as well as methoxytrimethylsilane, ethoxytrimethylsilane , methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorodimethylsilane, chlorodimethylvinylsilane, chlorotrimethylsilane, dimethylsilanol, dimethylvinylsilanol, trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, and the like. Organic compounds that give the structural unit (1-5) include 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, methanol, ethanol and the like. of alcohol. According to the above description, compositions containing such monomers for obtaining silsesquioxane derivatives are also provided.

Alcohol can be used as a reaction solvent in the condensation step. Alcohol is a narrowly defined alcohol represented by the general formula R--OH, and is a compound having no functional groups other than an alcoholic hydroxyl group. Specific examples include, but are not limited to, 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 -pentanol, 2-ethyl-2-butanol, 2,3-dimethyl-2-butanol, cyclohexanol and the like. 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 step, these alcohols can be used singly or in combination of two or more. More preferred alcohols are compounds capable of dissolving the required concentration of water in the condensation step. Alcohols with such properties are compounds having a water solubility of 10 g or more per 100 g of alcohol at 20°C.

The alcohol used in the condensation step is 0.5% by mass or more with respect to the total amount of all reaction solvents, including the amount added during the hydrolysis / polycondensation reaction, so that the resulting silsesquioxane derivative gelation can be suppressed. The amount used is preferably 1% by mass or more and 60% by mass or less, 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 sub-solvent. The co-solvent may be either a polar solvent, a non-polar solvent, or a combination of both. Preferred polar 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 a co-solvent, it is preferably used in an amount of 5% by mass or less of the total reaction solvent. A preferred polar solvent is 2-propanol, which is industrially available at a low cost. By using 2-propanol in combination with the alcohol of the present invention, the alcohol of the present invention can be converted to water at a concentration necessary for the hydrolysis step. can be dissolved in the required amount of water together with the polar solvent, and the effect of the present invention can be obtained. A preferable amount of the polar solvent is 20 parts by weight or less, more preferably 1 to 20 parts by weight, particularly preferably 3 to 10 parts by weight, based on 1 part by weight of the alcohol according to the present invention.

Non-polar solvents include, but are not limited to, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, alcohols, ethers, amides, ketones, esters, cellosolve, and the like. . Among these, aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons are preferred. Such a non-polar solvent is not particularly limited, but for example, n-hexane, isohexane, cyclohexane, heptane, toluene, xylene, methylene chloride, etc. are preferable because they azeotrope with water, and when these compounds are used together, After the condensation step, when the reaction solvent is removed by distillation from the reaction mixture containing the silsesquioxane derivative, water and a polymerization catalyst such as an acid dissolved in water can be efficiently distilled off. As the non-polar solvent, xylene, which is an aromatic hydrocarbon, is particularly preferred because of its 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 step proceeds in the presence of water. The amount of water used for hydrolyzing the hydrolyzable groups contained in the raw material monomer is preferably 0.5 to 5 mol, more preferably 1 to 2 mol, relative to the hydrolyzable groups. Moreover, the hydrolysis/polycondensation reaction of the raw material monomer may be carried out without a catalyst, or may be carried out using a catalyst. An acid or an alkali is used as a catalyst in the hydrolysis/polycondensation reaction. As such catalysts, acid catalysts exemplified by, for example, inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid; and 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 an amount corresponding to 0.01 to 20 mol%, and an amount corresponding to 0.1 to 10 mol%, relative to the total amount of silicon atoms contained in the raw material monomer. It is more preferable to have

Completion of the hydrolysis/polycondensation reaction in the condensation step can be appropriately detected by the methods described in the above-mentioned various publications. In addition, in the condensation step for producing the silsesquioxane derivative, an auxiliary agent can be added to the reaction system. Examples thereof include antifoaming agents for suppressing foaming of the reaction solution, scale control agents for preventing scale deposition on reaction vessels and stirring shafts, polymerization inhibitors, hydrosilylation reaction inhibitors, and the like. The amount of these auxiliaries to be 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 step in the production of the silsesquioxane derivative, a distillation step is provided to remove the reaction solvent and by-products, residual monomers, water, etc. contained in the reaction solution obtained from the condensation step. The stability and usability of the oxane derivative can be improved. In particular, by using a solvent azeotropic with water as the reaction solvent and simultaneously distilling off, the acid or base used as the polymerization catalyst can be efficiently removed. For the distillation, depending on the boiling point of the solvent used, etc., a temperature of 100° C. or lower and reduced pressure conditions can be used as appropriate.

(Layered compound)
The composition may contain a layered compound. The layered compound is not particularly limited, and one or more known layered compounds can be used. Layered compounds include, for example, silicate layered compounds such as talc (layered magnesium silicate), boron nitride, and minerals such as mica and smectite. Among them, talc and boron nitride are mentioned.

Layered compounds are generally in powder form. The particle shape is not particularly limited. Also, the average particle size is not particularly limited, but is preferably 10 μm or less, for example. This is because good oxidation resistance is obtained when the thickness is 10 μm or less. More preferably, it is 5 μm or less. Moreover, it is more preferably 3 μm or less, and still more preferably 2.5 μm or less. Also, the lower limit thereof is not particularly limited, but is, for example, 0.5 μm or more, and is, for example, 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 size of the layered compound means a particle size D50 corresponding to a cumulative frequency of 50% by volume from fine particles having a smaller particle size in a volume-based particle size distribution based on a laser diffraction/scattering method. do. For the measurement, a dispersion liquid in which a layered compound such as talc is dispersed using ultrasonic waves can be used.

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

(oxygen storage material)
The composition can include an oxygen storage material. An oxygen storage material is a material having oxygen storage capacity. _The oxygen storage material is not particularly limited, and known oxygen storage materials can be used. Examples include alumina, titania, zirconia, ceria, iron oxide ( _Fe2O3 ), ceria-zirconia composite oxide, Certain perovskite-type metal oxides and the like are included. Zirconia and ceria-zirconia composite oxides may be stabilized with a known stabilizer. The oxygen storage material may be such a metal oxide doped with other metal atoms. As the oxygen storage material, for example, ceria, zirconia, and ceria-zirconia composite oxide can be preferably used. As the oxygen storage material, one or a combination of two or more of such known oxygen storage materials can be used.

Oxygen storage materials are generally in powder form. The particle shape in the powder is not particularly limited. Also, the average particle size is not particularly limited, but is preferably 5 μm or less, for example. If it is 5 μm or less, it is considered that the surface area exhibits a high oxygen storage capacity. More preferably, it is 1 μm or less. Further, it is more preferably 500 nm or less, more preferably 100 nm or less, still more preferably 50 nm or less, still more preferably 30 nm or less, and still more preferably 20 nm or less.

In this specification, when the average particle size of the oxygen storage material is less than 1 μm, the particle size is calculated after obtaining the specific surface area by the BET method. That is, ^{the specific surface area (m 2} _/ g , S), the average particle size can be determined. In addition, in measuring the amount of nitrogen gas adsorbed, the gas is adsorbed at 77K to the sample which has been degassed at 300°C under vacuum for 12 hours or longer. When the average particle size is 1 μm or more, it is calculated by a laser diffraction/scattering method, which is explained for the average particle size of the layered compound.

The content of the oxygen storage material in the present composition is not particularly limited, and can be an effective amount that suppresses oxidation of the silsesquioxane derivative used. The oxygen storage material is, for example, 0.05% by mass or more, or, for example, 0.1% by mass or more, or, for example, 0.5% by mass or more, or for example, based on the total mass of the silsesquioxane derivative and the oxygen storage material. It can be 1% by weight or more, for example 3% by weight or more, for example 5% by weight or more, for example 10% by weight or more, or for example 15% by weight or more. Moreover, it can be, for example, 25% by mass or less, or, for example, 20% by mass or less with respect to the total amount. In addition, the content of the oxygen storage material is, for example, 0.05% by mass or more and 50% by mass or less, or for example, 0.1% by mass or more and 40% by mass with respect to the total mass of the silsesquioxane derivative and the oxygen storage material. % by mass or less.

The composition can include either or both of the layered compound and the oxygen storage material. When both are contained, their unique effects act to effectively suppress the oxidation of the silsesquioxane derivative, and excellent heat resistance can be obtained. Even when both of them are contained, they can be contained within the respective content ranges already described. Further, 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 is is, for example, 10% by mass or more and 80% by mass or less, for example, 15% by mass or more and 70% by mass or less, or for example, 20% by mass or more and 60% by mass or less.

(Aspect of the present composition)
The present composition can adopt various aspects. The present composition includes, for example, an uncured (not crosslinked or polymerized by a polymerizable functional group) silsesquioxane derivative, and the composition (typically in an amorphous form such as a liquid) before film formation or molding. body.)

The present composition may also be, for example, a composition such as a film-like or molded product formed on the surface of the object to be processed, containing the cured product of the silsesquioxane derivative.

(Composition containing uncured silsesquioxane derivative)
The composition of this aspect can 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. Furthermore, an initiator and/or a polymerization catalyst (curing agent) necessary for curing and polymerization can be included as necessary. Since the present composition comprises a layered compound and/or an oxygen storage material together with an uncured silsesquioxane derivative, when the silsesquioxane derivative is exposed to heat, when it is cured by heating, or when the cured product When the silsesquioxane derivative or its cured product is exposed to heat, the silsesquioxane derivative or its cured product is made heat resistant. Moreover, a solvent can be included as another component.

(Polymerization initiator)

The composition can contain a polymerization initiator for polymerizing the silsesquioxane derivative through the polymerizable functional group. The type of polymerization initiator varies depending on the type of polymerizable functional group provided in the silsesquioxane derivative, but various initiators and curing agents such as photoinitiators, thermal initiators and radical polymerization initiators can be used. . Those skilled in the art can appropriately select the type and amount of the polymerization initiator and curing agent in consideration of the polymerizable functional group to be used and the application of the present composition. For example, known organic peroxides, azo compounds, and the like can be used as radical polymerization initiators.

Examples of organic peroxides include benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, paramenthane hydroperoxide, di-t-butyl peroxide and the like. Azo compounds include azobisisobutyronitrile, azobisisovaleronitrile, azobisisocapronitrile and the like.

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

(hydrosilylation catalyst)
When the polymerizable functional group has an unsaturated organic group in the presence of a hydrosilyl hydrogen atom, the hydrosilylation catalyst used for curing (hydrosilylation) of the silsesquioxane derivative by hydrosilylation includes, for example, cobalt, nickel, Simple substances of group 8 to group 10 metals such as ruthenium, rhodium, palladium, iridium and platinum, organic metal complexes, metal salts, metal oxides and the like can be mentioned. A platinum-based catalyst is usually used. Examples of platinum-based catalysts include cis-PtCl ₂ (PhCN) ₂ , platinum carbon, platinum complexes coordinated with 1,3-divinyltetramethyldisiloxane (Pt(dvs)), platinum vinylmethyl cyclic siloxane complexes, platinum carbonyl- Vinylmethyl cyclic siloxane complex, tris(dibenzylideneacetone)diplatinum, chloroplatinic acid, bis(ethylene)tetrachlorodiplatinum, cyclooctadienedichloroplatinum, bis(cyclooctadiene)platinum, bis(dimethylphenylphosphine)dichloroplatinum , tetrakis(triphenylphosphine)platinum, and the like. Among these, platinum complexes coordinated with 1,3-divinyltetramethyldisiloxane (Pt(dvs)), platinum vinylmethyl cyclic siloxane complexes, and platinum carbonyl-vinylmethyl cyclic siloxane complexes are particularly preferred. In addition, Ph represents a phenyl group. The amount of the catalyst used is preferably 0.1 mass ppm or more and 1000 mass ppm or less, more preferably 0.5 to 100 mass ppm, relative to the amount of the silsesquioxane derivative, and 1 to 50 mass ppm. Mass ppm is more preferred.

When the present composition contains a catalyst for the hydrosilylation reaction, the hydrosilylation reaction may take precedence over the dehydration polycondensation of the residual alkoxy group or hydroxyl group in the structural unit (1-5). and the alkoxy group or hydroxyl group may be provided so as to allow further cross-linking reaction.

When the present 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 inhibitors include methylvinylcyclotetrasiloxane, acetylene alcohols, siloxane-modified acetylene alcohols, hydroperoxides, and hydrosilylation inhibitors containing nitrogen, sulfur or phosphorus atoms. .

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

(solvent)
The silsesquioxane derivative can be used as it is, or if necessary, it can be diluted with a solvent and used for film formation. The solvent is preferably a solvent that dissolves the silsesquioxane derivative, examples of which include aromatic hydrocarbon solvents, chlorinated hydrocarbon solvents, alcohol solvents, ether solvents, amide solvents, ketone solvents, ester solvents, and cellosolve solvents. and various organic solvents such as aliphatic hydrocarbon solvents. In the presence of a hydrosilylation catalyst such as Pt, a solvent other than alcohol is preferred in order to avoid decomposition of the Si—H group.

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

A film having excellent heat resistance can be formed by supplying the present composition to the surface of a workpiece having an arbitrary shape and curing the composition. For example, the composition can be applied to the surface of the work site and then the composition cured.

The supply of the present composition to the surface of the object to be processed is not particularly limited, but for example, ordinary coating methods such as spray coating, casting, spin coating and bar coating can be used.

(Composition containing cured product of silsesquioxane derivative)
The present composition can also be a composition containing a cured product obtained by polymerizing and curing a silsesquioxane derivative having a polymerizable functional group. Such compositions may also contain layered compounds and/or oxygen storage materials. The present composition is, for example, a composition 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.

As a cured product of the silsesquioxane derivative, unreacted alkoxy groups in the silsesquioxane derivative, that is, alkoxy groups and hydroxyl groups of R ⁴ in the structural unit (1-5) are sufficiently dehydrated and polycondensed to form siloxane bonds. (The curing by polycondensation of such residual alkoxy groups is also referred to as primary curing.) cured by further promoting cross-linking. Such a cured product (hereinafter also referred to as a primary cured product) can be included in the silsesquioxane derivative represented by the compositional formula (1).

Other cured products of silsesquioxane derivatives are cured by promoting cross-linking through reactions with polymerizable functional groups provided in structural units (1-2) to (1-4) (such curing is also referred to as secondary curing. ) can be mentioned. Such a cured product (hereinafter also referred to as a secondary cured product) is obtained by polymerizing at least part of the polymerizable functional groups in these structural units in the silsesquioxane derivative based on the inherent polymerizability of the functional groups. can include derivatives of silsesquioxane derivatives having structural moieties such as

Other cured products of silsesquioxane derivatives promote cross-linking by causing a hydrosilylation reaction between the hydrogen atoms provided in the structural units (1-2) to (1-4) and the unsaturated organic groups. A cured product obtained by curing (such curing is also referred to as secondary curing) is exemplified. In such a cured product (hereinafter also referred to as a secondary cured product), at least a part of the functional groups (hydrosilyl groups and unsaturated organic groups) that undergo hydrosilylation reaction in these structural units of the silsesquioxane derivative undergo hydrosilylation reaction. Structural moieties containing carbon-carbon bonds (single or double bonds) derived from unsaturated organic groups (-Si-C-C-Rm-Si-, -Si-C=C-Rm- Si—) (also referred to herein as a hydrosilylation structural moiety, where R is, for example, an organic group having 1 to 8 carbon atoms and m is an integer of 0 or 1). Derivatives of derivatives can be included.

When the composition is film-formed, the composition is generally a secondary cured product of a silsesquioxane derivative. In addition to the polymerized portion by the polymerizable functional group, the hydrosilylated structural portion can contribute to practical film strength and film performance.

A primary cure of a silsesquioxane derivative may be accompanied by a secondary cure, and a secondary cure may be accompanied by a primary cure, but a secondary cure is often accompanied by a primary cure. Therefore, cured products of silsesquioxane derivatives are generally secondary cured products, often accompanied by primary curing. A typical cured product is characterized by the presence or absence of a crosslinked structure due to secondary curing. The cured product is detected by, for example, ¹ H NMR, ²⁹ Si NMR, Q units, T units, D units and M units, structural units such as alkoxy groups, and structural regularity (irregularity), and IR The composition and structure can be specified by detecting the characteristic group by spectrum.

The composition contains only the silsesquioxane derivative or a cured product thereof, and may contain other components as necessary.

(Oxidation suppression 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 comprise a step of heating a silsesquioxane derivative or a cured product thereof together with a layered compound and/or an oxygen storage material. can. The method for inhibiting oxidation is also a method for increasing the heat resistance of the silsesquioxane derivative or its cured product. In the various aspects of the present composition described above, in the step of producing a silsesquioxane derivative cured product and the step of heating the cured product, a silsesquioxane derivative or a cured product thereof using a layered compound and/or an oxygen storage material oxidation is suppressed. Therefore, by providing such a step, oxidation of the silsesquioxane derivative or its cured product is suppressed, and heat resistance is improved.

In view of the above, the present specification provides 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 active ingredients.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is by no means limited to this example. Further, the viscosity of the obtained silsesquioxane derivative was measured at 25°C using an E-type viscometer.

Moreover, in the following description, both parts and % represent parts by mass and % by mass.

(Preparation of silsesquioxane derivative-containing composition and cured product thereof)
Silsesquioxane derivative having a methacryloyl group in the T unit (manufactured by Toagosei Co., Ltd., MAC-SQ TM-100, viscosity 4000 mPa s) 70 parts and talc (Japan talc, SG95, D50 = 2.5 μm) 30 parts And 0.7 parts of a thermal radical initiator (NOF, Vertible E, t-butyl peroxy-2-ethylhexyl monocarbonate) are weighed into a vial and mixed at 1800 rpm for 1 minute using a rotation or revolution mixer. , to obtain the composition of Test Example 1.

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

The specimens were held in air at 350° C. for 1 hour, 24 hours, and in a nitrogen atmosphere at 350° C. for 24 hours, and the tensile shear strength was measured on the specimens 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 test piece was also measured for tensile shear during heating at 200°C. The tensile speed was set to 10 mm/min. Table 1 shows the results.

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 as a test piece of Comparative Example A. In addition, a composition containing bisphenol A type epoxy resin: talc (75 parts: 25 parts) was prepared, and this 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. Obtained. The test pieces of Comparative Examples 1 and 2 were also subjected to the same temperature treatment, and the tensile shear strength of the test pieces before and after the treatment was measured. The results are shown in Table 1 together.

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

(Thermal Behavior of Silsesquioxane Derivative-Containing Composition)
(Preparation of silsesquioxane derivative (liquid, uncured curable composition) composition)
70 parts of the same silsesquioxane derivative (MAC-SQ TM-100) used in Example 1 and 30 parts of talc (Japan talc, D50 = 1 μm, 2.5 μm and 5 μm) were mixed. Three curable compositions (liquids) were prepared.

(Preparation of silsesquioxane derivative (cured product) composition)
70 parts of a silsesquioxane derivative (MAC-SQTM-100), 30 parts of talc (SG25, Nippon Talc, D50 = 2.5 μm), and 0.7 parts of a thermal radical initiator (NOF, Vertible E), A 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 further heated at 150 ° C. for 1 hour. It was heated for a period of time and thermally cured to obtain a cured product A.

In addition, the same cisylsesquioxane derivative, talc (SG95) and ceria-zirconia composite oxide (average particle size 5 to 10 nm) are mixed at a mass ratio of 7:3:1, respectively, and a thermal radical initiator ( NOF and Vertible E) 0.7 parts are mixed, the same operation as in Example 1 is performed to prepare a thermosetting composition B, and the thermosetting composition B is cured by heat in the same manner as the thermosetting composition B. I got item B.

Furthermore, the same silsesquioxane derivative and 0.7 parts of a radical initiator (NOF, Vertible E) were treated in the same manner as in Example 1 to prepare a control thermosetting composition, which was sandblasted. It was applied to an aluminum plate, heated at 120° C. for 1 hour (DK63, manufactured by Yamato Scientific Co., Ltd.), further heated at 150° C. for 1 hour, and thermally cured to obtain a control cured product.

(Evaluation of thermal behavior)
The thermal behavior of the three liquid compositions MAC-SQ TM-100 alone and was evaluated by TGA. The results are shown in Figure 1. Compositions were prepared and the thermal behavior of these compositions was evaluated by TGA. Furthermore, the thermal behavior of the cured product of the bisphenol A type epoxy resin was also evaluated. The results are shown in FIG. In addition to the actual measurement values of mass changes (%) of various compositions, FIG. The weight change rate is also described together with the weight change rate of the composition.

The thermal behavior of the A, B and control cures was evaluated by TGA. The results are shown in FIG. FIG. 2(a) shows the weight change rate from 0.degree. C. to 1000.degree.

As shown in FIG. 1, the addition of talc shifts the weight loss start temperature indicating oxidation of the silsesquioxane derivative-containing composition (liquid, uncured curable composition) to a higher temperature side, and the polymerization loss temperature increases. It was found that the temperature shifted to the higher temperature side by 20°C or more than the bisphenol A type epoxy resin. Also, when the average particle size of talc was 1 to 5 μm, the weight loss temperature shifted to the high temperature side. When TGA was performed on these compositions even in nitrogen, there was no difference between the presence or absence of talc.

In addition, as shown in FIG. 2, it was found that the polymerization decrease initiation temperature indicating oxidation also shifted to the high temperature side for the silsesquioxane derivative cured product.

From the above, it was found that the improvement in heat resistance due to the layered compound such as talc and/or the oxygen storage material is due to the suppression of oxidation of the silsesquioxane derivative (uncured) and its cured product. In addition to talc, it was found that addition of an oxygen storage material such as a ceria-zirconia composite oxide further suppresses oxidation.

(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 in Example 1. In addition, except that the components shown in the table below were used in each part, the same operations as in Test Example 1 of Example 1 were performed to prepare the compositions of Test Examples 1 to 17, and prepare each test piece. bottom.

(Comparative Examples 1 to 3 of Cured Products of Silsesquioxane Derivatives Only or Silsesquioxane Derivatives and Other Components)
A composition of Comparative Example 1 was prepared in the same manner as in Example 1, and a test piece was prepared. were performed to prepare the compositions and specimens of Comparative Examples 2 and 3.

(Comparative Examples 4 and 5 of Cured Epoxy Resins)
The same procedure as in Example 1 for Comparative Example 2 was performed to prepare compositions and test specimens for Comparative Examples 4 and 5.

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

A tensile shear strength test was performed according to Example 1 on the test pieces before and after the temperature treatment. A tensile shear test during heating at 200° C. was also performed on some of the test pieces. Table 2 shows the results.

Note that notation in the table will be explained below.
MAC-SQ TM-100: methacryloyl group-containing radical-curable silsesquioxane derivative (manufactured by Toagosei Co., Ltd.)
AC-SQ TA-100: acryloyl group-containing radical-curable silsesquioxane derivative (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 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 size 2-3 μm (manufactured by Wako Pure Chemical Industries, Ltd.)
Ceria-zirconia composite oxide: CeO ₂ /ZrO ₂ , average particle size 5-10 nm
Ceria 1: CeO ₂ , average particle size 5-10 nm
Ceria 2: CeO ₂ , average particle size 5.5 μm
Zirconia: ZrO ₂ , average particle size 10-15 nm
Ferric oxide: Fe ₂ O ₃ , average particle size of 50 nm or less Perbutyl E: t-butylperoxy-2-ethylhexyl monocarbonate (manufactured by NOF Co., Ltd.)

D50 of talc was measured using SALD200 (manufactured by Shimadzu Corporation) using a dispersion liquid obtained by dispersing talc using ultrasonic waves. A commercially available particle size distribution analyzer based on a laser diffraction/scattering method can be used. The average particle size of the hexagonal boron nitride was also defined as D50, which was measured based on the particle size distribution obtained by the laser diffraction/scattering method.

The average particle size of ceria-zirconia composite oxide, ceria ₁ , zirconia and ferric oxide is determined by the BET method (multipoint The average particle size was obtained from the specific surface area (m ² /g, S) obtained by analysis according to the method). In addition, in measuring the nitrogen gas adsorption amount, each sample was degassed at 300° C. under vacuum for 12 hours or longer, and then gas was adsorbed at 77K. In addition, ceria 2 was measured by a laser diffraction/scattering method in the same manner as talc, etc., due to the particle size.

As shown in Table 2, the test pieces (test examples 1 to 5) bonded with the cured silsesquioxane derivative cured containing only the layered compound, the derivative cured containing the layered compound and the oxygen storage material Test pieces adhered with the cured product (Test Examples 6 to 16) and test pieces adhered with the derivative cured product cured containing only the oxygen storage material (Test Example 17) both before and after the temperature treatment: A decrease in tensile shear strength was excellently suppressed. 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 cured silsesquioxane derivative, and the cured silsesquioxane derivative containing other components Compared with the same rate of change in Comparative Examples 2 and 3 using the material and Comparative Example 4 using the epoxy resin, the test pieces of the test examples using the layered compound and/or the oxygen storage material have a tensile shear strength at 350 ° C. It was found that the decrease was well suppressed. Moreover, even if silica, calcium carbonate, or the like was added, it was the same as not adding it at all. As minerals that are a kind of layered compound, mica and smectite were each cured in the same manner as in Test Example 1, and the adhesive strength was measured in the same manner. also confirmed.

Furthermore, according to Test Examples 6 to 16, which contain both a layered compound and an oxygen storage material, the inclusion of both is effective in suppressing a decrease in tensile shear strength after heat treatment (increasing heat resistance), and these are synergistic. found to be working effectively. In addition, it was found that a high heat resistance effect can be obtained even if the temperature is maintained at 350°C for 1 hour, or if the temperature is maintained at 200°C or 250°C for a long time. In addition, it was found that almost the same effect of increasing heat resistance was obtained for silsesquioxane derivatives having an acryloyl group even if the polymerizable functional group was a methacryloyl group.

Furthermore, with respect to the layered compound, as shown in Test Examples 1 to 5, a sufficient effect was obtained by using 3 parts of the silsesquioxane derivative with respect to 7 parts of the silsesquioxane derivative. The heat-resistant effect will be exhibited in a range of, for example, 5% to 50%, preferably 10% to 40%, more preferably 20% to 40%, relative to the total mass of the layered compound. have understood. As for 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. , more effective if 0.4% or more, more effective if 10% or more, and still more effective if 20% or more. Moreover, even when the amount added was 30%, sufficient adhesive strength was exhibited. From the above, the oxygen storage material is, for example, 0.07% or more and 30% or less, preferably 0.4% or more and 20% or less, with respect to the total mass of the silsesquioxane derivative and the oxygen storage material. found that it can be done. In addition, when the layered compound and the oxygen storage material are included, sufficient adhesive strength can be maintained even if the total mass of the silsesquioxane derivative, the tank-like compound, and the oxygen storage material exceeds 40%. have understood.

In addition, the oxygen storage material exhibited a heat-resistant effect on the silsesquioxane derivative cured product, but did not sufficiently exhibit a heat-resistant effect on the epoxy resin.

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

In addition, it was found that talc and hexagonal boron nitride, which are layered compounds, both exhibited an excellent heat resistance effect, but the heat resistance effect was greater when the average particle size was small. That is, when the average particle size exceeds 5 μm, the heat resistance effect tends to vary. Therefore, it was found that the layered compound preferably has an average particle size of less than 5 μm, preferably 4 μm or less, more preferably 3 μm or less.

Moreover, it was found that the oxygen storage materials of Examples 1 to 5 and Comparative Example 1 exhibited higher heat resistance. Among the oxygen storage materials, it was found that the ceria-zirconia composite oxide, which has a high oxygen storage capacity, has the highest oxidation resistance. Also, in the oxygen storage material, if the average particle size exceeds 5 μm, the oxidation resistance tends to decrease. The average particle size of the oxygen storage material is preferably less than 5 μm, more preferably 4 μm or less. It was found that the thickness is more preferably 3 μm or less, still more preferably 2 μm or less, and still more preferably 1 μm or less.

(Thermal behavior of other cured silsesquioxane derivative compositions)
As the silsesquioxane derivative, the following silsesquioxane derivative having an oxetanyl group in the SiO _1.5 unit (OX-SQ, TX-100, manufactured by Toagosei Co., Ltd., hereinafter referred to as silsesquioxane A) and the like , talc ( _SG95 ) and ceria-zirconia composite oxide (average particle size 5 to 10 nm) were mixed at a mass ratio of 7:3:1 to prepare compositions (liquid), and the thermal behavior of these compositions was evaluated by TGA. In addition, TGA was performed in the same manner only for silsesquioxanes A and B. The results are shown in FIG. In addition, in FIG. 3, based on the actual measurement of the mass change (%) of silsesquioxanes A and B, the mass change was multiplied by 0.63 to offset the presence of talc and the like in the composition. The respective mass changes of sesquioxanes A and B are shown.

As shown in FIG. 3, it was found that the addition of talc and ceria-zirconia composite oxide shifted the weight loss start temperature, which indicates the oxidation of the silsesquioxane derivative curing, to the higher temperature side.

From the above, it was found that the layered compound and the oxygen storage material similarly exhibit the oxidation-inhibiting action and the heat-resistant action even in the silsesquioxane cured product having such a polymerizable functional group.

Claims (10)

Formula (1) below:

(In formula (1), w and x are positive numbers, v, y and z are 0 or positive numbers, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a carbon represents an alkenyl group having 1 to 10 atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or a polymerizable functional group, and each R2 is independently a hydrogen atom, an alkyl having 1 to 10 carbon atoms group, 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; 10 alkyl group, alkenyl group having 1 to 10 carbon atoms, alkynyl group having 1 to 10 carbon atoms, aryl group, aralkyl group or a polymerizable functional group; R4 is a hydrogen atom; and at least one of R1, two R2 and three R3 represents a polymerizable functional group, except when all polymerizable functional groups are vinyl groups.)
A silsesquioxane derivative represented by
a layered compound;
an oxygen storage material ;
contains
The oxygen storage material is one or more selected from the group consisting of ceria, zirconia and ceria-zirconia composite oxide,
A curable silsesquioxane derivative composition in which the silsesquioxane derivative is cured with polymerization and/or cross-linking by at least the polymerizable functional group. 2. The composition according to claim 1, wherein said layered compound is one or more selected from the group consisting of talc and boron nitride. 3. The composition of claim 1 or 2, wherein the layered compound is talc. The composition according to any one of claims 1 to 3, wherein the layered 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 is contained 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 composition according to any one of claims 1 to 5, wherein the oxygen storage material is a ceria-zirconia composite oxide. 7. The composition according to any one of claims 1 to 6, wherein the oxygen storage material is contained 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 composition according to any one of claims 1 to 7, wherein the polymerizable functional group comprises a (meth)acryloyl group, an oxetanyl group or an epoxy group. The composition according to any one of claims 1 to 8, which is used for forming a heat-resistant film. Formula (1) below:

(In formula (1), w and x are positive numbers, v, y and z are 0 or positive numbers, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a carbon represents an alkenyl group having 1 to 10 atoms, an alkynyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or a polymerizable functional group, and each R2 is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; group, 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; 10 alkyl group, alkenyl group having 1 to 10 carbon atoms, alkynyl group having 1 to 10 carbon atoms, aryl group, aralkyl group or a polymerizable functional group; R4 is a hydrogen atom; and at least one of R1, two R2 and three R3 represents a polymerizable functional group, except when all polymerizable functional groups are vinyl groups.)
A cured product obtained by curing the silsesquioxane derivative represented by at least the silsesquioxane derivative with polymerization and / or crosslinking by the polymerizable functional group ,
a layered compound;
an oxygen storage material;
contains
The silsesquioxane derivative cured product composition, wherein the oxygen storage material is one or more selected from the group consisting of ceria, zirconia and ceria-zirconia composite oxides.

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