WO2020080081A1

WO2020080081A1 - Silsesquioxane derivative composition and use of same

Info

Publication number: WO2020080081A1
Application number: PCT/JP2019/038571
Authority: WO
Inventors: 賢明岩瀬; 武士藤田
Original assignee: 東亞合成株式会社
Priority date: 2018-10-18
Filing date: 2019-09-30
Publication date: 2020-04-23
Also published as: TW202035570A; CN112888715B; JPWO2020080081A1; KR20210068108A; KR102640556B1; CN112888715A; JP7276348B2

Abstract

In order to improve the heat resistance of a silsesquioxane derivative, the present invention provides a silsesquioxane derivative composition which contains a silsesquioxane derivative and a layered compound.

Description

Silsesquioxane derivative composition and use thereof

The present specification relates to a composition containing a silsesquioxane derivative and its use.

(Cross-reference of 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, and is described in this Japanese application. All content provided shall be incorporated.

Silsesquioxane is a compound having a unit represented by RSiO _1.5 as a structural unit and having a three-dimensional crosslinked structure by a siloxane bond, and R may have various functional groups including an organic functional group. it can. Such silsesquioxane derivatives (silsesquioxane derivatives) are known as excellent heat resistant materials (Patent Documents 1 and 2). Since the silsesquioxane derivative is an inorganic-organic hybrid material, it can exhibit organic characteristics such as flexibility and solubility in addition to the inorganic characteristics such as heat resistance. For example, a certain type of silsesquioxane derivative is used as a curable adhesive or the like because it has a polymerizable functional group such as an epoxy group as an organic group (Patent Document 3).

International Publication No. 2005/10077 International Publication No. 2009/66608 JP, 2008-95819, A

According to the present inventors, the organic group included in the silsesquioxane derivative is oxidized depending on the conditions such as the atmosphere and the heating temperature, whereby the original mechanical properties such as mechanical properties at high temperature are deteriorated. It was found that the properties of silsesquioxane can change.

However, no technology has been reported to suppress the oxidation of organic groups in silsesquioxane. Moreover, since silsesquioxane is known to have high heat resistance, an effective technique for further improving the heat resistance has not been provided. Furthermore, at present, there is no study on a technique for ensuring heat resistance under severe conditions such that the organic group in silsesquioxane is oxidized.

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

The present inventors focused on the possibility 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 the oxidation of the silsesquioxane derivative, and as a result, the heat resistance of the silsesquioxane derivative can be improved. The present specification provides the following means based on these findings.

[1] a silsesquioxane derivative,
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,
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 oxide.
[9] The composition according to any one of [6] to [8], wherein the oxygen storage material is a ceria-zirconia composite oxide.
[10] Any 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 based on 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 comprising:
[14] A method for suppressing oxidation of a silsesquioxane derivative or a cured product thereof, which comprises a step of heating the silsesquioxane derivative together with the layered compound and / or the oxygen storage material.
[15] A step of heating the silsesquioxane derivative together with the layered compound and / or the oxygen storage material,
A method of increasing the heat resistance of a silsesquioxane derivative or a cured product thereof.
[16] An oxidation inhibitor for a silsesquioxane derivative or a cured product thereof, which comprises a layered compound and / or an oxygen storage material as an active ingredient.
[17] A heat resistance improver for a silsesquioxane derivative or a cured product thereof, which comprises a layered compound and / or an oxygen storage material as an active ingredient.

It is a figure which shows the thermal behavior of the silsesquioxane derivative which has a methacroyl group. It is a figure which shows the thermal behavior of the hardened | cured material of a silsesquioxane derivative. It is a figure which shows the thermal behavior of the other silsesquioxane derivative which has an oxetanyl group and an epoxy group.

The disclosure of the present specification relates to a technique of 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, and thus improves the stability of the silsesquioxane derivative, particularly the stability against heat (heat resistance). Can be made. It is not always clear why the layered compound causes such an effect. It is considered that the gas barrier property and the gas diffusion inhibitory property of the layered compound are involved in the inhibition of the oxidation of the organic group.

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

The silsesquioxane derivative can have various organic groups, for example, can have a polymerizable functional group. When such a silsesquioxane derivative is polymerized, the decomposition of these polymerizable functional groups due to oxidation and the like may greatly affect the properties of the silsesquioxane derivative. Therefore, it is significant to impart oxidation resistance to a silsesquioxane derivative composition containing a silsesquioxane derivative having such a functional group and a cured product obtained by the composition by 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 the preferred examples of the present disclosure and is not intended to limit the scope of the present disclosure. Further, the additional features and inventions disclosed below may be used separately from or together with other features and inventions in order to provide a further improved “silsesquioxane derivative composition and use thereof”. You can

In addition, the combination of features and steps disclosed in the following detailed description is not essential in carrying out the present disclosure in the broadest sense, and is only for describing a representative specific example of the present disclosure. It is described. Furthermore, various features of the exemplary embodiments above and below, as well as those of the independent and dependent claims, are set forth herein in providing additional and useful embodiments of the present disclosure. It is not necessary to combine them according to the specific examples shown or in the order in which they are listed.

All the features described in the present specification and / or claims are separated from the configuration of the features described in the embodiments and / or claims individually as a limitation to the original disclosure of the application and the particular matter claimed, And are intended to be disclosed independently of each other. In addition, all numerical ranges and statements regarding groups or groups are intended to disclose the disclosure as originally filed and as limitations on the specific matter claimed, as well as intermediate constructions thereof.

Hereinafter, various embodiments of the technology for suppressing the oxidation of the silsesquioxane derivative according to the present disclosure and the use thereof will be described. Specifically, silsesquioxane derivative composition, silsesquioxane derivative cured product composition, silsesquioxane oxidation inhibition or heat resistance method, silsesquioxane oxidation inhibitor or heat resistance improver, etc. explain.

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

(Silsesquioxane derivative)
In the present specification, silsesquioxane is a polysiloxane having a main chain skeleton made of Si—O bonds and having (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).

The silsesquioxane derivative is represented by, for example, the following formula (1) having the structural units (1-1), (1-2), (1-3), (1-4) and (1-5). be able to. V, w, x, y and z in the formula (1) each represent the number of moles of the constituent units (1-1) to (1-5). In the 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 the silsesquioxane derivative.

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

The silsesquioxane derivative has five constitutional units in the formula (1), namely, the constitutional unit (1-1), the constitutional unit (1-2), the constitutional unit (1-3) and the constitutional unit (1-4). The constitutional unit selected from the above can be provided in combination so as to include at least one polymerizable functional group.

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

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

<Structural unit (1-2): T unit>
This structural unit defines the T unit as the 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, a C _1-10 alkyl group), an alkenyl group having 1 to 10 carbon atoms, and the number of carbon atoms. It may 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 unit include an organic group having 2 to 10 carbon atoms containing a hydrosilylatable carbon-carbon unsaturated bond included in the polymerizable functional group ( Hereinafter, when it is simply referred to as an unsaturated organic group), a crosslinking reaction between these units becomes possible.

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 the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. Such an alkyl group is, for example, a linear alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a methyl group, an ethyl group, It is a linear alkyl group having 1 to 4 carbon atoms such as propyl group and butyl group. Further, for example, 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 the alkenyl group include ethenyl (vinyl) group, orthostyryl group, metastyryl group, parastyryl group, 1-propenyl group, 2-propenyl (allyl) group, 1-butenyl group, 1-pentenyl group, 3-methyl group. Examples thereof include a 1-butenyl group, a phenylethenyl group, an allyl (2-propenyl) group and an octenyl (7-octen-1-yl) group.

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

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. Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.

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. Examples of the aralkyl group include phenylalkyl groups such as benzyl group.

R ¹ may be a polymerizable functional group. Examples of the polymerizable functional group include 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 and styryl group. However, methacryloyl group, acryloyl group, acryloyloxy group, methacryloyloxy group, α- Functions having methylstyryl group, vinyl ether group, vinyl ester group, acrylamide group, methacrylamide group, N-vinyl amide group, maleic acid ester group, fumaric acid ester group, N-substituted maleimide group, isocyanate group, oxetanyl group and epoxy group Groups and the like. Among them, a polymerizable functional group having a (meth) acryloyl group, an oxetanyl group and an epoxy group can be mentioned.

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

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.

The oxetanyl group is not particularly limited, and examples thereof include a (3-ethyl-3-oxetanyl) methyloxy group and a (3-ethyl-3-oxetanyl) oxy group. The group containing an 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. R ⁷ 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, and more preferably a propylene group.

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

The polymerizable functional group is the above-mentioned unsaturated organic group, that is, a functional group having a carbon-carbon double bond or a carbon-carbon triple bond capable of undergoing a hydrosilylation reaction with a hydrogen atom (hydrosilyl group) bonded to a silicon atom. 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 is polymerized with the hydrogen atom by a hydrosilylation reaction to form a hydrosilylated structural moiety. Specific examples of such unsaturated organic groups include the above-mentioned alkenyl groups and alkynyl groups. Although not particularly limited, for example, 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- Examples thereof include a propenyl) group and an octenyl (7-octen-1-yl) group. Such unsaturated organic groups are, for example, vinyl groups, parastyryl groups, allyl (2-propenyl) groups, octenyl (7-octen-1-yl) groups, and also vinyl groups, for example.

The silsesquioxane derivative as a whole may contain two or more polymerizable functional groups, in which case all the polymerizable functional groups may be the same as or different from each other. Moreover, a plurality of polymerizable functional groups may be the same and may further include different polymerizable functional groups.

The C _1-10 alkyl group, C _1-10 alkenyl group and C _1-10 alkynyl group may be substituted with aryl groups, aralkyl groups and polymerizable functional groups. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom, chlorine atom, 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, and other alkyl groups, hydroxy groups, alkoxy groups, aryloxy groups, aralkyloxy groups, and oxy groups (= It may be substituted with at least one of O), a cyano group and a protected hydroxyl group.

As the hydroxyl-protecting group of the protected hydroxyl group, a known hydroxyl-protecting group can be used without particular limitation. For example, as such a protecting group, an acyl-based protecting group represented by —C (═O) R (wherein R is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, An alkyl group having 1 to 6 carbon atoms such as an isobutyl group, an s-butyl group, a t-butyl group, and an n-pentyl group; or a phenyl group having a substituent or not having a substituent. The substituent of the phenyl group has a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group. , Alkyl groups such as n-heptyl group, n-octyl group and isooctyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy groups such as methoxy group and ethoxy group), trimethylsilyl group, triethyl A silyl protecting group such as a ryl group, a t-butyldimethylsilyl group and a t-butyldiphenylsilyl group; a methoxymethyl group, a methoxyethoxymethyl group, a 1-ethoxyethyl group, a tetrahydropyran-2-yl group and a tetrahydrofuran-2. An acetal-based protecting group such as an yl group; an alkoxycarbonyl-based protecting group such as a t-butoxycarbonyl group; a methyl group, an ethyl group, a t-butyl group, an octyl group, an allyl group, a triphenylmethyl group, a benzyl group, and ether-type protecting groups such as p-methoxybenzyl group, fluorenyl group, trityl group and benzhydryl group;

The silsesquioxane derivative may be provided with one kind or a combination of two or more kinds of the present structural unit. For example, it can be as one alkyl group of R ¹ in the structural unit, the R ¹ of one other constituent unit and a polymerizable functional group. Further, for example, it can be one of the unsaturated organic groups of R ¹ in the structural unit as a hydrogen atom, a R ¹ of one other constituent unit 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, and 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, and for example 0.9 or more And is, for example, 0.95 or more, and is, for example, 0.99 or more, and is, for example, 1.

<Structural unit (1-3): D unit>
This constitutional unit defines the D unit as the basic constitutional unit of the silsesquioxane derivative. R ^{2 of the} present structural unit is at least selected from the group consisting of 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. It can be one kind. R ^{2 s} in this structural unit may be the same or different.

With respect to 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 directly applied to the present structural unit.

The silsesquioxane derivative may be provided with one kind or a combination of two or more kinds of the present structural unit. In the silsesquioxane derivative, at least a part of the present structural units, for example, two R ² are both C _1-10 alkyl groups, and for example, all of the present structural units have two R ² All 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, for example, 0.3 or more, and for example, 0.35 or more, and for example, It is 0.4 or more. The same numerical value is, for example, 0.5 or less, and for example, 0.45 or less.

<Structural unit (1-4): M unit>
This structural unit defines the M unit as the basic structural unit of the silsesquioxane derivative. R ^{3 of the} present structural unit is at least selected from the group consisting of 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. It can be one kind. At least one selected from the group consisting of a hydrogen atom, a polymerizable functional group, and a C _1-10 alkyl group can be used. R ^{3 s} in this structural unit may be the same or different.

The silsesquioxane derivative may be provided with one kind or a combination of two or more kinds of the present structural unit. In the silsesquioxane derivative, at least a part of the present structural units, for example, two R ³ are both C _1-10 alkyl groups, and for example, all of the present structural units have two R ³ All 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. Although y is not particularly limited, for example, y / (v + w + x + y) is 0.25 or more, for example, 0.3 or more, and for example, 0.35 or more, and for example, It is 0.4 or more. The same numerical value is, for example, 0.5 or less, and for example, 0.45 or less.

<Structural 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 the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group and a hexyl group. Typically, it is an alkyl group having 2 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and is also an alkyl group having 1 to 6 carbon atoms.

The alkoxy group in the present structural unit is formed by replacing the "alkoxy group", which is a hydrolyzable group contained in the raw material monomer described later, or the alcohol contained in the reaction solvent, with the hydrolyzable group of the raw material monomer. An "alkoxy group" that remains in the molecule without being hydrolyzed or polycondensed. The hydroxyl group in the present structural unit is, for example, a hydroxyl group remaining in the molecule without being polycondensed 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 the formula (1), one or more of v, x and y are preferably positive numbers.

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

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

<Method for producing silsesquioxane derivative>
The silsesquioxane derivative can be produced by a known method. The method for producing a silsesquioxane derivative is described in WO 2005/010077, WO 2009/066608, 2013/099909, JP2011-052170A, JP2013-147659A. Are disclosed in detail as a method for producing polysiloxane.

The silsesquioxane derivative can be produced, for example, by the following method. That is, the method for producing a silsesquioxane derivative is provided with a condensation step of performing hydrolysis / polycondensation reaction of a raw material monomer which gives the constitutional unit in the above formula (1) by condensation in a suitable reaction solvent. it can. In this condensation step, a structural unit (1-2) is formed with a silicon compound having four siloxane bond-forming groups (hereinafter referred to as “Q monomer”) that forms the structural unit (1-1). 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 (hereinafter referred to as "D monomer") to form the structural unit (1-3). And a silicon compound (hereinafter, referred to as “M monomer”) forming a structural unit (1-4) having one siloxane bond-forming group.

In the present specification, specifically, a Q monomer forming the structural unit (1-1), a T monomer forming the structural unit (1-2), and a D monomer forming the structural unit (1-3). Also, at least the T monomer is used among the M monomers forming the structural unit (1-4). It is preferable to provide a distilling step of distilling off the reaction solvent, by-products, residual monomers, water and the like in the reaction solution after the raw material monomer is subjected to hydrolysis / polycondensation reaction in the presence of the reaction solvent.

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

In the synthesis of 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 instead of the D monomer. You can also

(In the above formulas (2) and (3), 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 aryl, and m and n are positive integers.)

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

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

R ⁹ and R ^{12 in 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 present in one molecule are the same group, May be different groups. Specific examples of R ⁹ and R ¹² are methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, cyclohexyloxy group, 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 and the like.

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

In the D oligomer, the number of repeating units 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, D monomer or D oligomer corresponding to each constitutional unit is an alkoxy group, and the siloxane bond-forming group contained in the M monomer is an alkoxy group or a siloxy group. It is preferable. Moreover, the monomer and oligomer corresponding to each structural unit may be used alone or in combination of two or more kinds.

Examples of the Q monomer that gives the structural unit (1-1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. Examples of the T monomer that provides the structural unit (1-2) include trimethoxysilane, triethoxysilane, tripropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, and ethyltrimethoxy. Examples thereof include silane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane and trichlorosilane. Examples of the T monomer that provides the structural unit (1-2) include trimethoxyvinylsilane, triethoxyvinylsilane, vinyltris (2-methoxyethoxy) silane, trimethoxyallylsilane, triethoxyallylsilane, and trimethoxy (7-octen-1-yl) silane. , (P-styryl) trimethoxysilane, (p-styryl) triethoxysilane, (3-methacryloyloxypropyl) trimethoxysilane, (3-methacryloyloxypropyl) triethoxysilane, (3-acryloyloxypropyl) trimethoxy Examples thereof include silane and (3-acryloyloxypropyl) triethoxysilane. Examples of the D monomer that provides the structural unit (1-3) include dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, diethoxydiethylsilane, dipropoxydimethylsilane, dipropoxydiethylsilane, dimethoxybenzylmethylsilane, diethoxybenzyl. Examples thereof include methylsilane, dichlorodimethylsilane, dimethoxymethylsilane, dimethoxymethylvinylsilane, diethoxymethylsilane and diethoxymethylvinylsilane. Examples of the M monomer that gives the structural unit (1-4) include 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, methoxytrimethylsilane, ethoxytrimethylsilane , Methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorodimethylsilane, chlorodimethylvinylsilane, chlorotrimethylsilane, dimethylsilanol, dimethylvinylsilanol, trimethylsilanol, triethylsilanol Tripropyl silanol, tributyl silanol and the like. Examples of the organic compound giving the structural unit (1-5) include 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, methanol and ethanol. Alcohol. According to the above description, a composition containing such a monomer for obtaining a silsesquioxane derivative is also provided.

In the condensation step, alcohol can be used as a reaction solvent. The alcohol is an alcohol in a narrow sense represented by the general formula R-OH, and is a compound having no functional group other than the alcoholic hydroxyl group. Although not particularly limited, specific examples thereof include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 2-butanol, 2-pentanol, 3-pentanol, 2-methyl-2-butanol and 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 can be exemplified. Among these, isopropyl alcohol, 2-butanol, 2-pentanol, 3-pentanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 3-methyl-2-pentanol, A secondary alcohol such as cyclohexanol is used. In the condensation step, these alcohols can be used alone or in combination of two or more. A more preferable alcohol is a compound capable of dissolving water in a concentration required in the condensation step. An alcohol having such a property is a compound 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 a silsesquioxane derivative produced by using 0.5% by mass or more of the total amount of all reaction solvents, including an additional amount added during the hydrolysis / polycondensation reaction. It is possible to suppress the gelation of. The preferred amount used 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 auxiliary solvent. The sub-solvent may be either a polar solvent or 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 the auxiliary solvent, the amount used is preferably 5% by mass or less of the whole reaction solvent. A preferred polar solvent is 2-propanol which is industrially available at a low cost, and when 2-propanol is used in combination with the alcohol according to the present invention, the alcohol according to the present invention has a concentration of water necessary for the hydrolysis step. Even when it is insoluble, it is possible to dissolve the required amount of water together with the polar solvent, and the effect of the present invention can be obtained. The amount of the polar solvent is preferably 20 parts by mass or less, more preferably 1 to 20 parts by mass, and particularly preferably 3 to 10 parts by mass with respect to 1 part by mass of the alcohol according to the present invention.

The non-polar solvent is not particularly limited, and examples thereof include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, alcohols, ethers, amides, ketones, esters and cellosolves. . Of these, aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons are preferable. The non-polar solvent is not particularly limited, but for example, n-hexane, isohexane, cyclohexane, heptane, toluene, xylene, methylene chloride and the like are preferable because they azeotrope with water, and when these compounds are used in combination. After the condensation step, when removing the reaction solvent from the reaction mixture containing the silsesquioxane derivative by distillation, the polymerization catalyst such as water and an acid dissolved in water can be efficiently distilled off. As the non-polar solvent, xylene which is 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, and particularly preferably 5 to 20 parts by mass with respect to 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 for hydrolyzing the hydrolyzable group contained in the raw material monomer is preferably 0.5 to 5 times mol, and more preferably 1 to 2 times mol, of the hydrolyzable group. The hydrolysis / polycondensation reaction of the raw material monomers may be carried out without a catalyst or using a catalyst. An acid or an alkali is used as a catalyst in the hydrolysis / polycondensation reaction. As such a catalyst, for example, an acid catalyst exemplified by inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid; organic acids such as formic acid, acetic acid, oxalic acid and paratoluenesulfonic acid is preferably used. The amount of the acid catalyst used is preferably 0.01 to 20 mol%, and more preferably 0.1 to 10 mol%, based on the total amount of silicon atoms contained in the raw material monomers. More preferably.

The completion of the hydrolysis / polycondensation reaction in the condensation step can be appropriately detected by the methods described in the various publications mentioned above. In addition, an auxiliary agent can be added to the reaction system in the condensation step in the production of the silsesquioxane derivative. Examples thereof include an antifoaming agent that suppresses foaming of the reaction solution, a scale control agent that prevents scale adhesion to the reaction canister and the stirring shaft, a polymerization inhibitor, a hydrosilylation reaction inhibitor, and the like. The amount of these auxiliaries used is arbitrary, but is preferably about 1 to 10 mass% with respect to the concentration of the silsesquioxane derivative in the reaction mixture.

After the condensation step in the production of the silsesquioxane derivative, the reaction solution and the by-products contained in the reaction solution obtained by the condensation step, the residual monomer, the distilling step for distilling off water, etc. The stability and usability of the oxane derivative can be improved. In particular, by using a solvent that is azeotropic with water as the reaction solvent and distilling off at the same time, the acid or base used as the polymerization catalyst can be efficiently removed. It should be noted that, although it depends on the boiling point of the solvent used and the like, the pressure may be appropriately reduced at a temperature of 100 ° C. or lower.

(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. Examples of the layered compound include silicate layered compounds such as talc (layered magnesium silicate), boron nitride, 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. The average particle size is also 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 μm or less. Further, it is more preferably 3 μm or less, and further preferably 2.5 μm or less. The lower limit is not particularly limited, but is, for example, 0.5 μm or more, and is 1.0 μm or more. The average particle size of the layered compound can be measured by a laser diffraction / scattering method. In the present specification, the average particle diameter of the layered compound refers to a particle diameter D50 corresponding to a cumulative frequency of 50% by volume from the fine particle side having a small particle diameter in the volume-based particle size distribution based on the laser diffraction / scattering method. To do. In 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 composition is not particularly limited, and may 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, for example 15% by mass or more, and for example 20% by mass or more, and for example 25% with respect to the total mass of the silsesquioxane derivative and the layered compound. The content may be, for example, 30% by mass or more, or 30% by mass or more. Further, it can be, for example, 50% by mass or less, or 45% by mass or less, or 40% by mass or less with respect to the total amount. 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, or the like with respect to the total mass of the silsesquioxane derivative and the layered compound. It can be 20% by mass or more and 40% by mass or less.

(Oxygen storage material)
The composition can include an oxygen storage material. The oxygen storage material is a material having an oxygen storage capacity. The oxygen storage material is not particularly limited, and known oxygen storage materials can be used, for example, alumina, titania, zirconia, ceria, iron oxide (Fe ₂ O ₃ ), ceria-zirconia composite oxide, Examples include certain perovskite type metal oxides. The zirconia and ceria-zirconia composite oxide may be stabilized by a known stabilizer. The oxygen storage material may be such 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. As the oxygen storage material, such known oxygen storage materials can be used alone or in combination of two or more kinds.

Oxygen storage materials are generally in powder form. The particle shape of the powder is not particularly limited. The average particle size is also not particularly limited, but is preferably 5 μm or less, for example. It is considered that when the thickness is 5 μm or less, a high oxygen storage capacity is exhibited due to the surface area. 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, still more preferably 20 nm or less.

In the present specification, the average particle diameter of the oxygen storage material is calculated by determining the specific surface area by the BET method when the average particle diameter is less than 1 μm. That is, the specific surface area (m ² / g obtained by analyzing the gas adsorption amount measured by the gas adsorption method using nitrogen (N ₂ ) gas as an adsorbate by the BET method (multipoint method or one-point method) , S), the average particle diameter can be determined. When measuring the amount of nitrogen gas adsorbed, the sample degassed under vacuum at 300 ° C. for 12 hours or more is gas adsorbed at 77K. Further, when the average particle diameter is 1 μm or more, it is calculated by the laser diffraction / scattering method, which will be described with respect to the average particle diameter of the layered compound.

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

The composition may contain one or both of a layered compound and an oxygen storage material. When both are included, the respective unique effects act, and the oxidation of the silsesquioxane derivative is effectively suppressed, and excellent heat resistance can be obtained. Even when both are contained, they may be contained in the respective ranges of the content 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, relative to the total mass of the silsesquioxane derivative, the layered compound and the oxygen storage material. Can be, for example, 10% by mass or more and 80% by mass or less, or can be, for example, 15% by mass or more and 70% by mass or less, and can be, for example, 20% by mass or more and 60% by mass or less.

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

The composition may be, for example, a composition such as a film or a molded product which contains a cured product of a silsesquioxane derivative and is formed into a film on the surface of a workpiece.

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

(Polymerization initiator)

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

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

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

(Hydrosilylation catalyst)
When an unsaturated organic group is provided in the presence of a hydrogen atom of a hydrosilyl group as the polymerizable functional group, the hydrosilylation catalyst used for curing the silsesquioxane derivative by hydrosilylation (hydrosilylation) includes, for example, cobalt, nickel, Examples include ruthenium, rhodium, palladium, iridium, platinum, and other Group 8 to Group 10 metal simple substances, organic metal complexes, metal salts, metal oxides, and the like. Usually platinum-based catalysts are used. Platinum-based catalysts include cis-PtCl ₂ (PhCN) ₂ , platinum carbon, a platinum complex (Pt (dvs)) coordinated with 1,3-divinyltetramethyldisiloxane, a platinum vinylmethyl cyclic siloxane complex, platinum carbonyl. Vinylmethyl cyclic siloxane complex, tris (dibenzylideneacetone) diplatinum, chloroplatinic acid, bis (ethylene) tetrachlorodiplatinum, cyclooctadienedichloroplatinum, bis (cyclooctadiene) platinum, bis (dimethylphenylphosphine) dichloroplatinum And tetrakis (triphenylphosphine) platinum. Of these, particularly preferred are platinum complexes (Pt (dvs)) coordinated with 1,3-divinyltetramethyldisiloxane, platinum vinylmethyl cyclic siloxane complexes, and platinum carbonyl-vinylmethyl cyclic siloxane complexes. 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, and more preferably 1 to 50 mass% with respect to the amount of the silsesquioxane derivative. More preferably, it is ppm by mass.

When the 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). In some cases, the above-mentioned alkoxy group or hydroxyl group is provided so as to allow further crosslinking reaction.

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

The composition may be a composition for film formation or may be substantially free of a hydrosilylation catalyst. As described later, the silsesquioxane derivative can be cured by promoting the hydrosilylation reaction by heat treatment even in the absence of a hydrosilylation catalyst. In the present composition, substantially containing no hydrosilylation catalyst means not only the case where the hydrosilylation catalyst is not intentionally added, but the content of the hydrosilylation catalyst relative to the amount of the silsesquioxane derivative is, for example, , Less than 0.1 mass ppm, and for example, 0.05 mass ppm or less.

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

(Other ingredients)
Various additives may be further added to the composition before it is subjected to curing. Examples of the additive include a reactive diluent such as tetraalkoxysilane and trialkoxysilanes (trialkoxysilane, trialkoxyvinylsilane, etc.), and a polymerization functional group that is the same as or similar to the polymerizable functional group of the silsesquioxane derivative. Examples thereof include monomers and oligomers having a functional group. These additives are used within a range in which the obtained cured product of the silsesquioxane derivative does not impair the heat resistance.

It is possible to form a film having excellent heat resistance by supplying the composition to the surface of a workpiece having an arbitrary shape and curing the composition to form a film. For example, the composition can be applied to the surface of the site to be processed and then the composition cured.

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

(Composition containing cured product of silsesquioxane derivative)
The composition can also be a composition containing a cured product obtained by polymerizing and curing a silsesquioxane derivative having a polymerizable functional group with the polymerizable functional group. Such a composition can also contain a layered compound and / or an oxygen storage material. 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 a silsesquioxane derivative, an unreacted alkoxy group in the silsesquioxane derivative, that is, an alkoxy group or a hydroxyl group of R ⁴ in the structural unit (1-5) is dehydrated and polycondensed to sufficiently form a siloxane bond. Examples of the cured product include a cured product (which is also referred to as primary curing, which is cured by polycondensation of such residual alkoxy groups) by being further formed to promote crosslinking. Such a cured product (hereinafter, also referred to as a primary cured product) can be included in the silsesquioxane derivative represented by the composition formula (1).

The other cured product of the silsesquioxane derivative is cured by accelerating the cross-linking by the reaction of the polymerizable functional groups included in the structural units (1-2) to (1-4) (this curing is also referred to as secondary curing). .) The cured product. Such a cured product (hereinafter, also referred to as a secondary cured product) is obtained by polymerizing at least a part of the polymerizable functional groups in these constituent units in the silsesquioxane derivative based on the inherent polymerizability of the functional group. A derivative of the silsesquioxane derivative having the above-mentioned structural portion can be included.

The other cured product of the silsesquioxane derivative causes a hydrosilylation reaction between a hydrogen atom and an unsaturated organic group included in the structural units (1-2) to (1-4) to further promote crosslinking. A cured product that has been cured (the curing is also referred to as secondary curing) by doing so is given. Such a cured product (hereinafter, also referred to as a secondary cured product) has a functional group (hydrosilyl group and unsaturated organic group) which undergoes a hydrosilylation reaction in these constituent units in the silsesquioxane derivative, at least a part of which is hydrosilylated. Structural portion containing a carbon-carbon bond (single bond or double bond) derived from an unsaturated organic group formed by (-Si-C-C-Rm-Si-, -Si-C = C-Rm- Si-) (also referred to herein as a hydrosilylation structure moiety. 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 formed into a film, 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 structure portion can contribute to practical membrane strength and membrane performance.

The primary cure of the silsesquioxane derivative can be accompanied by a secondary cure, and the secondary cure can be accompanied by a primary cure, but the secondary cure is often accompanied by a primary cure. Therefore, the cured product of the silsesquioxane derivative is generally a secondary cured product, and is often accompanied by a primary cure. A typical cured product is characterized by the presence or absence of a crosslinked structure due to secondary curing. The cured product can be detected by, for example, ¹ H NMR or ²⁹ Si NMR, which is based on Q units, T units, D units and M units, structural units such as alkoxy groups, or regularity (irregularity) of the structure, and IR. The composition or structure can be specified by detecting the characteristic group by the 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 comprises a step of heating the silsesquioxane derivative or a cured product thereof together with the layered compound and / or the oxygen storage material. it can. At the same time, the method for suppressing oxidation is also a method for improving the heat resistance of the silsesquioxane derivative or a cured product thereof. 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, the silsesquioxane derivative or the cured product thereof with a layered compound and / or an oxygen storage material is used. Oxidation is suppressed. Therefore, by including such a step, oxidation of the silsesquioxane derivative or a cured product thereof is suppressed and heat resistance is improved.

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

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to this embodiment. Furthermore, the viscosity of the obtained silsesquioxane derivative was measured at 25 ° C. using an E-type viscometer.

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

(Preparation of silsesquioxane derivative-containing composition and cured product thereof)
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 30 parts of talc (Nippon Talc, SG95, D50 = 2.5 μm) And 0.7 part of a thermal radical initiator (NOF, Virtuable E, t-butylperoxy-2-ethylhexyl monocarbonate) were weighed into a vial and mixed for 1 minute at 1800 rpm using a rotation revolution mixer. A composition of Test Example 1 was obtained.

The composition of Test Example 1 was applied to a sandblasted aluminum plate, and likewise adhered to the sandblasted aluminum plate and heated at 120 ° C. for 1 hour (Yamato Scientific Co., Ltd., DK63), and then at 150 ° C. The test piece of Test Example 1 was obtained by heating for 1 hour and thermosetting.

The test piece was held in 350 ° C. air for 1 hour, 24 hours, and 350 ° C. nitrogen atmosphere for 24 hours, and the tensile shear strength of the test piece 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. The tensile shear of the test piece was also measured while heating at 200 ° C. The pulling speed was 10 mm / min in all cases. The results are shown in Table 1.

As a control, a composition was prepared in the same manner as in Test Example 1 using only the silsesquioxane derivative, and a test piece was prepared as a test piece of Comparative Example A. Further, a composition containing a bisphenol A type epoxy resin: talc (75 parts: 25 parts) was prepared, and the test piece of Comparative Example B was prepared by curing the composition at 120 ° C. for 1 hour and then at 150 ° C. for 1 hour. 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 together in Table 1.

As shown in Table 1, the test piece prepared from the silsesquioxane derivative containing talc (Test Example 1) was subjected to tensile shear in the test piece regardless of heating in air at 350 ° C. for 1 hour to several hours. The decrease in strength, that is, the decrease in adhesive strength was excellently suppressed. On the other hand, the test piece prepared with the silsesquioxane derivative to which talc was not added (Comparative Example A) and the mixed composition of the epoxy resin and talc (Comparative Example B) exhibited a significant decrease in tensile shear strength.

(Thermal Behavior of Composition Containing Silsesquioxane Derivative)
(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 (Nippon Talc, D50 = 1 μm, 2.5 μm and 5 μm) were mixed. Three curable compositions (liquid) 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, Virtuable 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) were mixed in a mass ratio of 7: 3: 1, and a thermal radical initiator ( 0.7 parts of Japanese fats and oils and Virtuable E) are mixed, and a thermosetting composition B is prepared by operating in the same manner as in Example 1. The thermosetting composition B is heat-cured and cured in the same manner as the thermosetting composition B. Item B was obtained.

Further, the same silsesquioxane derivative and 0.7 part of a radical initiator (Nippon Oil and Fats, Virtuable E) were operated in the same manner as in Example 1 to prepare a thermosetting composition as a control, and 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 were prepared into compositions shown in FIG. 1, 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. 1. In addition, in FIG. 1, in addition to the measured values of the mass change (%) of various compositions, an effective silsesquioxane derivative was obtained by multiplying the mass reduction of the silsesquioxane derivative containing no talc by 0.7. The change in weight was also shown together with the change in weight when the composition was the same as the composition.

The thermal behavior of the cured products A and B and the control cured product were evaluated by TGA. The results are shown in Figure 2. FIG. 2 (a) shows the rate of weight change from 0 ° C. to 1000 ° C., and FIG. 2 (b) shows the rate of weight change by expanding the temperature range from 300 ° C. to 600 ° C.

As shown in FIG. 1, the addition of talc shifts the weight reduction start temperature indicating oxidation of the silsesquioxane derivative-containing composition (liquid or uncured curable composition) to a high temperature side, and the polymerization reduction temperature It was found that the temperature was shifted to a temperature higher than the bisphenol A type epoxy resin by 20 ° C or more. Further, when the average particle diameter of talc was 1 to 5 μm, the weight reduction temperature was shifted to the high temperature side. When these compositions were subjected to TGA in nitrogen, no difference was observed with or without talc.

Also, as shown in FIG. 2, it was found that the polymerization reduction start temperature indicating oxidation of the cured product of the silsesquioxane derivative was shifted to the high temperature side.

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

(Test Examples 1 to 17 of cured product of silsesquioxane derivative and layered compound and / or oxygen storage material)
The composition and test piece of Test Example 1 were prepared in the same manner as in Example 1. Further, the same operations as in Test Example 1 of Example 1 were carried out except that the respective components shown in the following table were used to prepare the compositions of Test Examples 1 to 17 to prepare each test piece. did.

(Comparative Examples 1 to 3 of cured product of silsesquioxane derivative alone or silsesquioxane derivative and other components)
A composition of Comparative Example 1 was prepared in the same manner as in Example 1 to prepare test pieces, and the same operation as in Test Example 1 of Example 1 was carried out except that the components shown in the table below were used. The composition and test pieces of Comparative Examples 2 and 3 were prepared.

(Comparative Examples 4 to 5 of cured epoxy resin)
The same operations as in Comparative Example 2 of Example 1 were carried out to prepare the compositions and test pieces of Comparative Examples 4 and 5.

-A portion of these test pieces was heated at 350 ° C for 1 hour. Moreover, 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. 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 the temperature treatment in accordance with Example 1. A tensile shear test was also performed on some test pieces while heating at 200 ° C. The results are shown in Table 2.

The notations in the table will be described 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 diameter 2 to 3 μm (manufactured by Wako Pure Chemical Industries, Ltd.)
Ceria-zirconia composite oxide: CeO ₂ / ZrO ₂ , average particle size 5 to 10 nm
Ceria 1: CeO ₂ , average particle size 5 to 10 nm
Ceria 2: CeO ₂ , average particle size 5.5 μm
Zirconia: ZrO ₂ , average particle size 10 to 15 nm
Ferric oxide: Fe ₂ O ₃ , average particle size 50 nm or less Perbutyl E: t-butyl peroxy-2-ethylhexyl monocarbonate (manufactured by NOF Corporation)

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

The average particle size of the ceria-zirconia composite oxide, ceria 1, zirconia, and ferric oxide was measured by the gas adsorption method using nitrogen (N ₂ ) gas as an adsorbate, and the BET method (multipoint Method) to determine the average particle size from the specific surface area (m ² / g, S) obtained by analysis. In the measurement of the nitrogen gas adsorption amount, each sample was degassed under vacuum at 300 ° C. for 12 hours or more, and then gas adsorption was performed at 77K. In addition, ceria 2 was measured by the laser diffraction / scattering method in the same manner as talc and the like from the relationship of the particle size.

As shown in Table 2, test pieces (Test Examples 1 to 5) bonded with a silsesquioxane derivative cured product containing only a layered compound and cured, and a derivative cured with a layered compound and an oxygen storage material. The test pieces adhered with the cured product (Test Examples 6 to 16) and the test piece adhered with the derivative cured product containing only the oxygen storage material and cured (Test Example 17) were both before and after the temperature treatment. The 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 containing only the cured product of the silsesquioxane derivative, and curing of the silsesquioxane derivative containing other components In comparison with the same rate of change of Comparative Examples 2 to 3 and Comparative Example 4 using the epoxy resin, the test piece of the test example using the layered compound and / or the oxygen storage material shows a tensile shear strength at 350 ° C. It was found that the decrease was well suppressed. Moreover, even if silica, calcium carbonate, etc. were added, it was the same as not adding at all. In addition, when mica and smectite were used as minerals which are one of the layered compounds and cured products were obtained in the same manner as in Test Example 1 and the adhesive strength was measured in the same manner, the effect of adding the layered compound can be obtained. I also confirmed.

Furthermore, according to Test Examples 6 to 16 containing both the layered compound and the oxygen storage material, the inclusion of both of them is effective in suppressing the decrease in tensile shear strength after heat treatment (heat resistance), and these are synergistic. It was found to be working. It was also found that a high heat resistance effect can be obtained even at 350 ° C. for 1 hour or at 200 ° C. or 250 ° C. for a long time. It was also found that the silsesquioxane derivative having an acryloyl group, even if it was a methacryl group as a polymerizable functional group, had substantially the same heat resistance effect.

Further, as for the layered compound, as shown in Test Examples 1 to 5, since the use of 3 parts with respect to 7 parts of the silsesquioxane derivative was sufficient, it was confirmed that the layered compound was a silsesquioxane derivative. For example, 5% or more and 50% or less, preferably 10% or more and 40% or less, more preferably 20% or more and 40% or less, with respect to the total mass of the layered compound, the heat resistance effect may be exhibited. all right. Regarding the oxygen storage material, as shown in Test Examples 6 to 17, it is effective if the oxygen storage material is, for example, 0.007% or more based on the total mass of the silsesquioxane derivative and the oxygen storage material. It was found that 0.4% or more is more effective, 10% or more is more effective, and 20% or more is still effective. Further, even if 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. I found that I could do it. When the layered compound and the oxygen storage material are included, sufficient adhesive strength can be maintained even if the total amount of the silsesquioxane derivative, the tank-shaped compound, and the oxygen storage material exceeds 40%. all right.

Also, the oxygen storage material showed a heat resistance effect to the silsesquioxane derivative cured product, but did not show a sufficient heat resistance effect to the epoxy resin.

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

Moreover, both talc and hexagonal boron nitride, which are layered compounds, exhibited excellent heat resistance, but it was found that when the average particle size is small, the heat resistance is greater. 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, and more preferably 3 μm or less.

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

(Thermal Behavior of Other Silsesquioxane Derivative Cured Compositions)
As a silsesquioxane derivative, a silsesquioxane derivative having the following 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. In addition, talc (SG95) and ceria-zirconia composite oxide (average particle diameter) are used by using a cisilsesquioxane derivative having the following epoxy group in the SiO _1.5 unit (Toagosei Co., Ltd., hereinafter referred to as silsesquioxane B). 5 to 10 nm), and each was mixed at a mass ratio of 7: 3: 1 to prepare compositions (liquid), and thermal behavior of these compositions was evaluated by TGA. In addition, TGA was similarly performed only on the silsesquioxanes A and B. The results are shown in Fig. 3. In FIG. 3, the silsesquioxane A, B was used to offset the presence of talc or the like in the composition by multiplying the mass change by 0.63 based on the measured value of the mass change (%). The respective mass changes of sesquioxane 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 initiation temperature indicating oxidation of curing of the silsesquioxane derivative to the high temperature side.

From the above, it was found that the layered compound and the oxygen storage material similarly exhibited the oxidation suppressing effect and the heat resistance improving effect even in the silsesquioxane cured product having such a polymerizable functional group.

Claims

A silsesquioxane derivative,
A layered compound,
A silsesquioxane derivative composition containing:
The composition according to claim 1, wherein the layered compound is one or more selected from the group consisting of talc and boron nitride.
The composition according to 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 material 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, further containing an oxygen storage material.
A silsesquioxane derivative,
Oxygen storage material,
A silsesquioxane derivative composition containing:
The composition according to claim 6 or 7, wherein the oxygen storage material is one or more selected from the group consisting of ceria, zirconia, and ceria-zirconia composite oxide.
The composition according to any one of claims 6 to 8, wherein the oxygen storage material is a ceria-zirconia composite oxide.
The composition according to any one of claims 6 to 9, 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 a total mass of the silsesquioxane derivative and the oxygen storage material. .
The composition according to any one of claims 1 to 10, wherein the silsesquioxane derivative has a polymerizable functional group.
A silsesquioxane derivative having a polymerizable functional group,
A layered compound and / or an oxygen storage material,
A curable silsesquioxane derivative composition comprising:
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 comprising:
A method for suppressing oxidation of a silsesquioxane derivative or a cured product thereof, which comprises a step of heating the silsesquioxane derivative together with the layered compound and / or the oxygen storage material.
Heating the silsesquioxane derivative together with the layered compound and / or the oxygen storage material,
A method of increasing the heat resistance of a silsesquioxane derivative or a cured product thereof.
An oxidation inhibitor of a silsesquioxane derivative or a cured product thereof, which contains a layered compound and / or an oxygen storage material as an active ingredient.
A heat resistance improver for a silsesquioxane derivative or a cured product thereof, which contains a layered compound and / or an oxygen storage material as an active ingredient.