TW202035570A - Silsesquioxane derivative composition and use of same - Google Patents

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

Semi-siloxane derivative composition and its utilization

This manual is about the composition containing the semisiloxane derivative and its use.

(Cross-reference of related applications) This application is related to Japanese Patent Application No. 2018-1969510 of the Japanese invention patent application filed on October 18, 2018. The priority based on the Japanese application is claimed, and all the records in the Japanese application are incorporated. content.

Semisiloxane is a compound having a three-dimensional cross-linked structure formed by a siloxane bond with a unit represented by RSiO _1.5 as a structural unit. As R, various functional groups including organic functional groups can be provided. This semisiloxane derivative (semisiloxane derivative) is known as an excellent heat-resistant material (Patent Documents 1 and 2). In addition, since semisiloxane derivatives are inorganic-organic hybrid materials, in addition to inorganic properties such as heat resistance, they can also exhibit organic properties such as flexibility and solubility. For example, a certain semisiloxane derivative has a polymerizable functional group such as an epoxy group as an organic group, and is used as a curable adhesive or the like (Patent Document 3). [Prior Art Document] [Patent Document]

[Patent Document 1] International Publication No. 2005/10077 [Patent Document 2] International Publication No. 2009/66608 [Patent Document 3] Japanese Patent Application Publication No. 2018-95819

According to the inventors of the present invention, it is known that depending on conditions such as the ambient atmosphere or heating temperature, the organic groups possessed by the semisiloxane derivatives are oxidized, so that the mechanical properties at high temperatures are reduced, etc. The characteristics will change.

However, no technology has been reported that can inhibit the oxidation of organic groups in semisiloxane. In addition, it is known that the semisiloxane system has high heat resistance, and therefore no effective technology can be used to further improve its heat resistance. Moreover, the current situation is that there is no review of the technology that can ensure the heat resistance of organic groups such as semisiloxanes under severe conditions of oxidation.

This manual provides techniques and their utilization for enhancing heat resistance by inhibiting the oxidation of semisiloxane.

The inventors focused on the possibility of additives that can inhibit the oxidation of the organic groups in the semisiloxane derivatives, and explored such additives. As a result, it was found that both the layered compound and the oxygen storage material can inhibit the oxidation of the semisiloxane derivative, and as a result, the heat resistance of the semisiloxane derivative can be improved. This manual is based on such knowledge and insights and provides the following methods.

[1] A semi-siloxane derivative composition containing: Semisiloxane derivatives, and Layered compound. [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 average particle diameter of the layered compound is 5 μm or less. [5] The composition described in any one of [1] to [4] contains 5 mass% to 50 mass% of the layered compound relative to the total mass of the semisiloxane derivative and the layered compound Compound material. [6] The composition as described in any one of [1] to [5], which further contains an oxygen storage material. [7] A semi-siloxane derivative composition containing: Semisiloxane derivatives, and Oxygen storage material. [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] The composition according to any one of [6] to [9], which contains 0.1% by mass to 40% by mass relative to the total mass of the semisiloxane derivative and the oxygen storage material Oxygen storage material. [11] The composition according to any one of [1] to [10], wherein the semisiloxane derivative has a polymerizable functional group. [12] A sclerosing semisiloxane derivative composition, which has: Semi-siloxane derivatives with polymerizable functional groups, and Layered compounds and/or oxygen storage materials. [13] A hardened semi-siloxane derivative composition, which has: Cured products of semi-siloxane derivatives with polymerizable functional groups, and Layered compounds and/or oxygen storage materials. [14] A method for inhibiting the oxidation of a semisiloxane derivative or its cured product, which includes a step of heating the semisiloxane derivative together with a layered compound and/or an oxygen storage material. [15] A heat-resistant method of a semisiloxane derivative or its cured product, which includes a step of heating the semisiloxane derivative together with a layered compound and/or an oxygen storage material. [16] An oxidation inhibitor of a semisiloxane derivative or its hardened product, which uses layered compounds and/or oxygen storage materials as effective ingredients. [17] A heat resistance enhancer of a semisiloxane derivative or its hardened product, which uses a layered compound and/or an oxygen storage material as an effective ingredient.

[The form of implementing the invention]

The disclosure of this specification relates to a technique for further improving the heat resistance of the semisiloxane derivative by imparting oxidation resistance to the semisiloxane derivative. According to the disclosure of this specification, the presence of the layered compound suppresses the oxidation of the semisiloxane derivative, and further improves the stability of the semisiloxane derivative, especially the heat stability (heat resistance). The reason for such an effect by the layered compound is not necessarily obvious. It is considered that the gas barrier properties or gas diffusion inhibitory properties possessed by the layered compound are involved in the oxidation inhibition of the organic groups.

In addition, the present specification discloses that the presence of oxygen storage materials can inhibit the oxidation of the semisiloxane derivative, thereby improving the stability of the semisiloxane derivative, especially the heat stability (heat resistance). It is believed that such an effect is caused by the oxidation/reduction of the oxygen storage material itself or the adsorption of oxygen.

The semisiloxane derivative may have various organic groups, for example, may have a polymerizable functional group. When such a semisiloxane derivative is polymerized, the decomposition caused by oxidation of the polymerizable functional group may have a large influence on the properties of the semisiloxane derivative. Therefore, the layered compound and/or oxygen storage material imparts oxidation resistance to the semi-siloxane derivative composition containing the semi-siloxane derivative having the functional group and the cured product obtained from the composition The person is meaningful.

Hereinafter, the representative and non-limiting specific examples of the present disclosure will be described in detail with appropriate reference to the drawings. This detailed description is simply intended to show the industry in detail the preferred examples for implementing the present disclosure, and is not intended to limit the scope of the present disclosure. In addition, the additional features and inventions disclosed below are intended to provide a further improved "semisiloxane derivative composition and its utilization", and can be used separately or together with other features or inventions.

In addition, the combination of features or steps disclosed in the following detailed description is not necessary for implementing the present disclosure in the broadest sense, and is especially only used to describe the description of representative specific examples of the present disclosure. In addition, the various features of the above-mentioned and following representative specific examples and the various features described in the scope of independent and dependent patent applications are provided when additional and useful embodiments of the present disclosure are provided. It is not necessary to combine the specific examples described herein or the order listed.

All the features described in this specification and/or the scope of the patent application are not only the composition of the features described in the examples and/or the scope of the patent application, but also serve as limitations on the original disclosure of the application and the specific matters in the requested scope , The intention is to reveal individually and independently of each other. Furthermore, the description of all numerical ranges and groups or collectives serves as a limitation for the disclosure of the original application and the specific items in the requested range, and has the intention of revealing their intermediate composition.

Hereinafter, various embodiments of the oxidation suppression technology of the semisiloxane derivative of the present disclosure and its utilization will be described. Specifically, a description will be given of the semi-siloxane derivative composition, the semi-siloxane derivative cured product composition, the oxidation inhibitor or heat-resistant method of semi-siloxane, the oxidation inhibitor or heat resistance enhancer of semi-siloxane Wait.

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

(Semisiloxane derivatives) In this specification, the so-called semisiloxane is a polysiloxane whose main chain skeleton is composed of Si-O bonds and composed of (RSiO _1.5 ) units. The semisiloxane derivative in this specification is a compound having one or more units represented by such polysiloxane and (RSiO _1.5 ) (T unit).

Semisiloxane derivatives, for example, may have structural units (1-1), (1-2), (1-3), (1-4), and (1-5) represented by the following formula (1) . Each of v, w, x, y, and z in the formula (1) represents the number of moles of the structural unit of (1-1) to (1-5). In addition, in formula (1), v, w, x, y, and z mean the average value of the ratio of the number of moles of each structural unit contained in one molecule of the semisiloxane derivative.

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

The semisiloxane derivative is based on the five structural units in the formula (1), which is composed of the structural unit (1-1), the structural unit (1-2), the structural unit (1-3) and the structural unit (1- 4) The selected structural unit may contain at least one polymerizable functional group in combination.

In addition, the semisiloxane derivative contains at least the structural unit (1-2). The semisiloxane derivative may also contain the constituent unit (1-2) and the constituent unit (1-3). For example, in formula (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. In addition, the semisiloxane derivative may be composed only of the structural unit (1-2) (w is positive, and the others are 0).

<Construction Unit (1-1): Q Unit> This structural unit is represented by formula (1) and defines the Q unit as the basic structural unit of polysiloxane. The number system of this structural unit in a semisiloxane derivative is not specifically limited.

<Construction unit (1-2): T unit> This construction unit is defined as the T unit which is the basic structural unit of polysiloxane. R ^{1 in} this structural unit may be selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms (hereinafter also referred to as C _1-10 alkyl groups), alkenyl groups having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. At least one of 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 are provided with an organic group containing carbon-carbon unsaturated bonds and containing 2 to 10 carbon atoms (hereinafter also When only called unsaturated organic group), it becomes capable of cross-linking reaction between these units.

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

R ¹ may be C _1-10 alkenyl. The C _1-10 alkenyl group may be any of an aliphatic group, an alicyclic group, and an aromatic group, and may also be any of linear and branched. Specific examples of alkenyl groups include vinyl (ethenyl, vinyl) groups, o-styryl groups, methyl styryl groups, p-styryl groups, 1-propenyl groups, and 2-propenyl (allyl) groups. , 1-butenyl, 1-pentenyl, 3-methyl-1-butenyl, phenylvinyl, allyl (2-propenyl) group, octenyl (7-octene-1 -Base) base and so on.

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

R ¹ may be an aryl group. The number of carbon atoms is, for example, 6 or more and 20 or less, or for example, 6 or more and 10 or less. As an aryl group, a phenyl group, 1-naphthyl group, 2-naphthyl group, etc. are mentioned.

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

R ¹ may be a polymerizable functional group. As the polymerizable functional group, for example, a polymerizable functional group that can be cured by heat or light is used. The polymerizable functional group is not particularly limited, and it also includes the above-mentioned functional groups such as vinyl, allyl, and styryl. Examples include methacrylic groups, acrylic groups, and acrylic groups. Methacryloxy, α-methylstyryl, vinyl ether, vinyl ester, acrylamide, methacrylamide, N-vinylamino, maleate, rich Functional groups such as maleate group, N-substituted maleimide group, isocyanate group, oxetanyl group and epoxy group. In particular, a polymerizable functional group having a (meth)acryloyl group, an oxetanyl group, and an epoxy group can be mentioned.

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

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 include (3-ethyl-3-oxetanyl)methoxy, (3-ethyl-3-oxetanyl)oxy Base etc. The oxetanyl group-containing group is preferably a group represented by the following formula or a group containing the group.

In the above formula, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbons, and R ⁸ represents an alkylene group having 1 to 6 carbons. As R ⁷ , a hydrogen atom, a methyl group, and an ethyl group are preferable, and an ethyl group is more preferable. 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. Examples thereof include β-glycidoxyethyl, γ-glycidoxypropyl, γ-glycidoxybutyl, etc. Alkyl group with 1 to 10 carbon atoms, epoxypropyl group, β-(3,4-epoxycyclohexyl)ethyl group, γ-(3,4-epoxycyclohexyl)propyl group substituted by oxy group , Β-(3,4-epoxycycloheptyl)ethyl, 4-(3,4-epoxycyclohexyl)butyl, 5-(3,4-epoxycyclohexyl)pentyl, etc. The oxysilyl group is an alkyl group with 1-10 carbons substituted by a cycloalkyl group with 5-8 carbons.

The polymerizable functional group may be the above-mentioned unsaturated organic group, that is, a functional group having a hydrogen atom (hydrosilyl) bonded to a silicon atom and a carbon-carbon double bond or a carbon-carbon triple bond capable of hydrosilation reaction. The unsaturated organic group also functions as a polymerizable functional group due to the presence of the hydrogen atom in the hydrogen silyl group, and the hydrogen atom is polymerized by the hydrosilation reaction to form a hydrosilation structure part. As a specific example of this unsaturated organic group, the above-mentioned alkenyl group, alkynyl group, etc. are mentioned. Although not particularly limited, for example, vinyl, o-styryl, methyl styryl, p-styryl, acrylic, methacryl, acryloxy, methacryloxy , 1-propenyl, 1-butenyl, 1-pentenyl, 3-methyl-1-butenyl, phenylvinyl, ethynyl, 1-propynyl, 1-butynyl, 1 -Pentynyl, 3-methyl-1-butynyl, phenylbutynyl, allyl (2-propenyl) group, octenyl (7-octen-1-yl) group, etc. The unsaturated organic group is, for example, vinyl group, p-styryl group, allyl (2-propenyl) group, octenyl (7-octen-1-yl) group, and, for example, vinyl group.

In addition, the entire semisiloxane derivative may contain two or more types of polymerizable functional groups, and at that time, all the polymerizable functional groups may be the same or different from each other. In addition, the plural polymerizable functional groups are the same, and may further include different polymerizable functional groups.

C _1-10 alkyl, C _1-10 alkenyl, C _1-10 alkynyl aryl, aralkyl, and polymerizable functional group may be substituted. As the substituent, halogen atoms such as fluorine atom, chlorine atom, bromine atom, chlorine atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, Alkyl, hydroxyl, alkoxy, aryloxy, aralkoxy and oxy (=O), such as tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, etc. At least one of the cyano group and the protected hydroxyl group is substituted.

The protecting group of the hydroxyl group having a protected hydroxyl group is not particularly limited, and a well-known hydroxyl protecting group can be used. For example, as the protecting group, a protecting group of the acyl group represented by -C(=O)R (wherein R represents methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, second butyl, tertiary butyl, n-pentyl and other C1-C6 alkyl groups; or, substituted or unsubstituted phenyl groups; as substituted phenyl groups Substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n- Alkyl groups such as octyl and isooctyl groups; halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, etc.; alkoxy groups such as methoxy and ethoxy groups, etc.), trimethylsilyl, triethylsilyl , Tertiary butyl dimethyl silyl, tertiary butyl diphenyl silyl and other silicon protecting groups; methoxymethyl, methoxyethoxymethyl, 1-ethoxyethyl , Tetrahydropiperan-2-yl, tetrahydrofuran-2-yl and other acetal protecting groups; tertiary butoxycarbonyl and other alkoxycarbonyl protecting groups; methyl, ethyl, tertiary Protective groups such as ether-based, octyl, allyl, triphenylmethyl, benzyl, p-methoxybenzyl, stilbene, trityl, benzhydryl, etc.

The semisiloxane derivative can be provided by combining one or two or more of this structural unit. For example, the present R & lt an alkyl group as ^a constituent unit, a constituent unit to ^another, R ¹ as the polymerizable functional group. In addition, for example, it may be an unsaturated organic group in which R ^{1 of} one structural unit is regarded as a hydrogen atom, and R ^{1 of} another structural unit is regarded as a polymerizable functional group.

The ratio w of the molar number of the present constituent unit in the semisiloxane derivative is a positive number. The w series is not particularly limited, but for example, w/(v+w+x+y) is 0.25 or more, for example, 0.3 or more, for example, 0.35 or more, for example, 0.4 or more, for example, 0.5 or more, for example It is 0.6 or more, for example, 0.7 or more, for example, 0.8 or more, for example, 0.9 or more, for example, 0.95 or more, for example, 0.99 or more, or for example, 1.

<Construction unit (1-3): D unit> This construction unit is defined as the D unit which is the basic structural unit of the semisiloxane derivative. R ^{2 in} this structural unit may be 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. At least one of them. R ² in this structural unit may be the same or different.

Regarding 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, various aspects already described can be directly applied to this structural unit.

The semisiloxane derivative can be provided by combining one or two or more of this structural unit. At least a part of the present structural unit of the semisiloxane derivative is, for example, two R ² are all C _1-10 alkyl groups, and for example, all the present structural unit is two R ² are all C _1-10 alkyl groups.

The ratio x of the molar number of the present constituent unit in the semisiloxane derivative is 0 or a positive number. The x system is not particularly limited, but for example, x/(v+w+x+y) is 0.25 or more, for example, 0.3 or more, for example, 0.35 or more, for example, 0.4 or more. The same value is, for example, 0.5 or less, or for example, 0.45 or less.

<Construction unit (1-4): M unit> This construction unit is defined as the M unit which is the basic structural unit of the semisiloxane derivative. R ^{3 in} this structural unit may be 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 At least one of them. It may be at least one selected from the group consisting of a hydrogen atom, a polymerizable functional group, and a C _1-10 alkyl group. R ³ in this structural unit may be the same or different.

Regarding 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, various aspects already described can be directly applied to this structural unit.

The semisiloxane derivative can be provided by combining one or two or more of this structural unit. At least a part of the present structural unit of the semisiloxane derivative is, for example, two R ³ are all C _1-10 alkyl groups, and for example, all the present structural unit is two R ³ are all C _1-10 alkyl groups.

The ratio y of the molar number of the present constituent unit in the semisiloxane derivative is 0 or a positive number. The y system is not particularly limited, but for example, y/(v+w+x+y) is 0.25 or more, for example, 0.3 or more, for example, 0.35 or more, for example, 0.4 or more. The same value is, for example, 0.5 or less, or for example, 0.45 or less.

<Constructive Unit (1-5)> This structural unit specifies a unit containing an alkoxy group or a hydroxyl group in the semisiloxane 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 any one of an aliphatic group and an alicyclic group, and may be either linear or branched. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, and hexyl. Typically, it is an alkyl group having 2 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, and another example is an alkyl group having 1 to 6 carbon atoms.

The alkoxy group in this structural unit is the "alkoxy group" of the hydrolyzable group contained in the raw material monomer described later or the "alkoxy group" generated by the substitution of the alcohol contained in the reaction solvent with the hydrolyzable group of the raw material monomer "It does not undergo hydrolysis or polycondensation but remains in the molecule. In addition, the hydroxyl group "alkoxy group" in the present structural unit does not undergo polycondensation after hydrolysis, and the hydroxyl group in the molecule remains.

The ratio z of the molar number of the present constituent unit in the semisiloxane derivative is 0 or a positive number.

Among the semisiloxane derivatives, it is preferable to have one or more kinds selected from the group consisting of the structural unit (1-1), the structural unit (1-3) and the structural unit (1-4) . That is, in the formula (1), one or more of v, x, and y are preferably positive numbers.

＜Molecular weight etc.＞ The number average molecular weight of the semisiloxane derivative is preferably in the range of 300 to 10,000. Such semisiloxane derivatives are inherently low-viscosity, easily soluble in organic solvents, the viscosity of the solution is also easy to handle, and the storage stability is excellent. In consideration of coating properties, 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, and more preferably 300 to 2,000. Preferably it is 500-2,000. 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 semisiloxane derivative is preferably liquid. When the semisiloxane derivative is liquid, the viscosity at 25°C is, for example, 500 mPa·s or more, preferably 1,000 mPa·s or more, and more preferably 2000 mPa·s or more, from the viewpoint of filler mixing.

＜Method of producing semisiloxane derivatives＞ Semisiloxane derivatives can be produced by well-known methods. The method for producing semisiloxane derivatives is described in International Publication No. 2005/010077 Pamphlet, Same Pamphlet No. 2009/066608, Same Pamphlet No. 2013/099909, Japanese Patent Publication No. 2011-052170, Japanese Patent Open 2013-147659 bulletin etc. disclose in detail as a manufacturing method of polysiloxane.

The semisiloxane derivative can be produced by the following method, for example. That is, the method for producing a semisiloxane derivative may include a condensation step of performing hydrolysis and polycondensation reaction of the raw material monomer of the constituent unit in the above formula (1) by condensation in an appropriate reaction solvent. In this condensation step, a silicon compound having 4 siloxane bond forming groups (hereinafter referred to as Q monomer") forming the constituent unit (1-1), and the constituent unit (1-2) having 3 A silicon compound with two siloxane bond forming groups (hereinafter referred to as "T monomer"), and a silicon compound with two siloxane bond forming groups (hereinafter referred to as "D monomer") forming the constituent unit (1-3) ") and a silicon compound (hereinafter referred to as "M monomer") forming a structural unit (1-4) having one siloxane bond generating group.

In this specification, specifically, the Q monomer which forms the structural unit (1-1), the T monomer which forms the structural unit (1-2), the D monomer which forms the structural unit (1-3) and the formation structure are used specifically At least T monomer among M monomers in unit (1-4). After subjecting the raw material monomer to the hydrolysis and polycondensation reaction in the presence of the reaction solvent, it is preferable to include a distillation step of distilling off the reaction solvent, by-products, residual monomers, water, etc. from the reaction liquid.

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

In addition, in the synthesis of semisiloxane derivatives, instead of D monomer, the following formula (2) and formula (3) shown in the following formula (2) and formula (3) of the siloxane compound having a siloxane bond forming group (hereinafter also Called D oligomer).

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

The siloxane bond forming group of D oligomer refers to the atom or group of atoms that can form siloxane bond with the silicon atom in the silane compound. Specific examples are methoxy and ethoxy. , N-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and other alkoxy groups, cyclohexyloxy and other cycloalkoxy groups, phenoxy and other aryloxy groups Groups, hydroxyl groups, hydrogen atoms, etc. The D oligomer shown in 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, it is easy to obtain a siloxane bond forming group with a hydroxyl group.

R ⁹ and R ^{12 of the} D oligomer are each an alkoxy group, an aryloxy group, an alkyl group, a cycloalkyl group, or an aryl group, and two R ⁹ and R ¹² existing in a molecule may be the same group. , It can also be a different base. Specific examples of R ⁹ and R ¹² are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, cyclohexyloxy, phenoxy Group, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, cyclohexyl, phenyl, etc.

The R ¹⁰ , R ¹¹ and R ^{13 of the} D oligomer are each an alkyl group, a cycloalkyl group or an aryl group. The plural R ¹⁰ and R ¹¹ in a molecule may be the same group or the same group. Different base. Specific examples of R ¹⁰ , R ¹¹ and R ¹³ are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, phenyl and the like. As D oligomers, multiple R ¹⁰ and R ^{11 in} one molecule are methyl groups or phenyl groups, which can be manufactured from inexpensive raw materials, and the cured product obtained by using this composition is excellent in adhesion, etc. It is more suitable, especially those with all methyl groups.

In the D oligomer, the number of repeating units m and n are positive integers. As the D oligomer, m and n are preferably 10-100, more preferably 10-50.

In the condensation step, the siloxane bond-forming group corresponding to the Q monomer, T monomer or D monomer or D oligomer of each constituent unit is preferably an alkoxy group, and the siloxane bond contained in the M monomer The generating group is preferably an alkoxy group or a siloxy group. Moreover, the monomer and oligomer system corresponding to each structural unit may be used individually, and may be used in combination of 2 or more types.

Examples of the Q monomer to be given to the structural unit (1-1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like. As the T monomer imparted to the structural unit (1-2), trimethoxysilane, triethoxysilane, tripropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyl Tripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane Cyclohexyl silane, cyclohexyl trimethoxy silane, cyclohexyl triethoxy silane, trichlorosilane, etc. Examples of the T monomer imparted to the constituent unit (1-2) include trimethoxyvinylsilane, triethoxyvinylsilane, vinyl ginseng (2-methoxyethoxy)silane, and trimethoxyvinylsilane. Allyl silane, triethoxy allyl silane, trimethoxy (7-octene-1-yl) silane, (p-styryl) trimethoxy silane, (p-styryl) triethyl Oxysilane, (3-methacryloxypropyl)trimethoxysilane, (3-methacryloxypropyl)triethoxysilane, (3-methacryloxypropyl)trimethyl Oxysilane, (3-propenyloxypropyl)triethoxysilane, etc. As the D monomer imparted to the constituent unit (1-3), dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, diethoxydiethyl Dimethylsilane, Dipropoxydimethylsilane, Dipropoxydiethylsilane, Dimethoxybenzylmethylsilane, Diethoxybenzylmethylsilane, Dichlorodimethylsiloxane, Dimethyl Oxymethyl silane, dimethoxymethyl vinyl silane, diethoxy methyl silane, diethoxy methyl vinyl silane, etc. As the M monomer that is given to the constituent unit (1-4), except for the hexamethyldisiloxane, hexaethyldisiloxane, and hexapropyldisilica which are given to the two constituent units (1-4) by hydrolysis Oxyane, 1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, methoxydimethylsiloxane , Ethoxy dimethyl silane, methoxy dimethyl vinyl silane, ethoxy dimethyl vinyl silane, but also methoxy trimethyl silane, ethoxy trimethyl silane , Methoxy dimethyl phenyl silane, ethoxy dimethyl phenyl silane, chloro dimethyl silane, chloro dimethyl vinyl silane, chlorotrimethyl silane, dimethyl silanol, dimethyl Vinylsilanol, trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, etc. Examples of the organic compound to be given to the constituent unit (1-5) include 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl -2-Propanol, methanol, ethanol and other alcohols. In accordance with the above description, a composition containing such a monomer for obtaining a semisiloxane derivative is also provided.

In the condensation step, alcohol can be used as a reaction solvent. The alcohol is a narrowly defined alcohol 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, as such specific examples, methanol, ethanol, n-propanol, isopropanol, 2-butanol, 2-pentanol, 3-pentanol, 2-methyl-2-butanol can be exemplified. Alcohol, 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, etc. Among these, isopropanol, 2-butanol, 2-pentanol, 3-pentanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol can be used , 3-methyl-2-pentanol, cyclohexanol and other secondary alcohols. In the condensation step, these alcohols may be used singly or in combination of two or more kinds. A more preferable alcohol is a compound that can dissolve water at the concentration necessary for the condensation step. Alcohols of this nature are compounds with a solubility of 10g or more per 100g of water at 20°C.

The alcohol used in the condensation step also includes the additional input part during the hydrolysis and polycondensation reaction. By using 0.5% by mass or more of the total amount of all reaction solvents, it is possible to suppress the formation of the semisiloxane derivative Gelation. A preferable usage amount is 1% by mass to 60% by mass, and more preferably 3% by mass to 40% by mass.

The reaction solvent used in the condensation step can be only alcohol, and can also be used as a mixed solvent with at least one type of auxiliary solvent. The auxiliary solvent may be any one of a polar solvent and a non-polar solvent, or a combination of the two. The polar solvent is preferably a secondary or tertiary alcohol having 3 or 7 to 10 carbon atoms, a diol having 2 to 20 carbon atoms, and the like. In addition, when a primary alcohol is used as a sub-solvent, it is preferable to use the amount to be 5 mass% or less of the entire reaction solvent. The preferred polar solvent is 2-propanol, which can be obtained inexpensively in industry. By using 2-propanol in combination with the alcohol of the present invention, even if the alcohol of the present invention cannot dissolve the necessary concentration of water in the hydrolysis step, A necessary amount of water can be dissolved together with a polar solvent to obtain the effects of the present invention. The amount of the polar solvent is preferably 20 parts by mass or less relative to 1 part by mass of the alcohol of the present invention, more preferably 1-20 parts by mass, and particularly preferably 3-10 parts by mass.

The non-polar solvent is not particularly limited, and examples include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, alcohols, ethers, amides, ketones, esters, and serosol. Among these, aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons are preferred. As such a non-polar solvent, it is not particularly limited. For example, n-hexane, isohexane, cyclohexane, heptane, toluene, xylene, dichloromethane, etc. are suitable for azeotroping with water. If these are used in combination For the compound, after the condensation step, when the reaction solvent is removed by distillation from the reaction mixture containing the semisiloxane derivative, the polymerization catalyst such as water and acid dissolved in water can be efficiently distilled off. As a non-polar solvent, in view of its relatively high boiling point, xylene which is an aromatic hydrocarbon is particularly preferred. The amount of the non-polar solvent used is 50 parts by mass or less, preferably 1-30 parts by mass, and particularly preferably 5-20 parts by mass relative to 1 part by mass of the alcohol of the present invention.

The hydrolysis/polycondensation reaction in the condensation step is carried out in the presence of water. In order to hydrolyze the hydrolyzable group contained in the raw material monomer, the amount of water used is preferably 0.5 to 5 times mol, and more preferably 1 to 2 times mol relative to the hydrolyzable group. In addition, the hydrolysis and polycondensation reaction of the raw material monomers can be carried out without a catalyst or can be carried out using a catalyst. The catalyst in the hydrolysis and polycondensation reaction is acid or alkali. As the catalyst, for example, inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid; and acid catalysts exemplified by organic acids such as formic acid, acetic acid, oxalic acid, and p-toluenesulfonic acid are preferably used. The amount of the acid catalyst used is relative to the total amount of silicon atoms contained in the raw material monomer, and is preferably an amount corresponding to 0.01-20 mol%, and more preferably an amount corresponding to 0.1-10 mol%.

The result of the hydrolysis/polycondensation reaction in the condensation step can be suitably detected by the methods described in the aforementioned various publications and the like. Furthermore, in the condensation step of the production of the semisiloxane derivative, an auxiliary agent may be added to the reaction system. For example, defoamers that suppress the foaming of the reaction liquid, scale control agents that prevent adhesion of scale to the reaction tank or stirring shaft, polymerization inhibitors, hydrosilation reaction inhibitors, and the like. The amount of these auxiliary agents used is arbitrary, but it is more preferably about 1 to 10% by mass relative to the concentration of the semisiloxane derivative in the reaction mixture.

After the condensation step in the production of the semi-siloxane derivative, it can be improved by having a step of distilling off the reaction solvent and by-products, residual monomers, water, etc. contained in the reaction solution obtained in the condensation step. The stability or usability of the generated semi-siloxane derivatives. 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. In addition, although it depends on the boiling point of the solvent used in the distillation, it can be at a temperature of 100°C or less, under reduced pressure conditions.

(Layered compound) The composition may contain a layered compound. The layered compound is not particularly limited, and one or two or more of well-known layered compounds can be used. Examples of the layered compound include silicate layered compounds such as talc (layered magnesium silicate), and minerals such as boron nitride, mica, or bentonite. In particular, talc or boron nitride can be cited.

The layered compound is generally in powder form. The particle shape is not particularly limited. In addition, the average particle size is not particularly limited, but, for example, it is preferably 10 μm or less. If it is 10 μm or less, good oxidation resistance can be obtained. More preferably, it is 5 μm or less. Furthermore, it is particularly preferably 3 μm or less, and even more preferably 2.5 μm or less. In addition, the lower limit is not particularly limited, but it is, for example, 0.5 μm or more, and for example, 1.0 μm or more. Furthermore, the average particle size of the layered compound can be measured by the laser diffraction and scattering method. In this specification, the average particle size of the layered compound is based on the volume-based particle size distribution based on the laser diffraction and scattering method. From the side of the particles with the smaller particle size, the cumulative frequency is 50% by volume. The particle size is called D50. In the measurement, a dispersion liquid of a layered compound such as talc dispersed by ultrasonic waves can be used.

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

(Oxygen storage material) This composition may contain an oxygen storage material. The oxygen storage material is a material with oxygen storage capacity. The oxygen storage material is not particularly limited, and well-known oxygen storage materials can be used, such as aluminum oxide, titanium oxide, zirconium oxide, cerium oxide, iron oxide (Fe ₂ O ₃ ), cerium oxide zirconium oxide composite oxide Material, a certain perovskite-type metal oxide, etc. In addition, zirconium oxide and ceria-zirconia composite oxide can be stabilized by a well-known stabilizer. The oxygen storage material may be a metal oxide doped with other metal atoms. As the oxygen storage material, for example, ceria, zirconia, and ceria-zirconia composite oxides can be preferably used. The oxygen storage material can be used in one type or a combination of two or more of such well-known oxygen storage materials.

The oxygen storage material is generally in powder form. The particle shape of the powder is not particularly limited. In addition, the average particle size is not particularly limited, but it is preferably 5 μm or less, for example. If it is 5 μm or less, it is judged that the surface area exhibits high oxygen storage ability. It is more preferably 1 μm or less, particularly preferably 500 nm or less, particularly preferably 100 nm or less, even more preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 20 nm or less.

In addition, in this specification, when the average particle diameter of the oxygen storage material is less than 1 μm, the particle diameter is calculated after the specific surface area is obtained by the BET method. That is, the gas adsorption amount measured by the gas adsorption method using nitrogen (N ₂ ) gas as the adsorbate is analyzed by the BET method (multi-point method or 1-point method), and the specific surface area (m ² /g , S), the average particle size can be obtained. In addition, in the measurement of the amount of nitrogen adsorption, the sample after degassing at 300°C under vacuum for 12 hours or more was allowed to adsorb gas at 77K. In addition, when the average particle size is 1 μm or more, it is calculated by the laser diffraction and scattering method described for the average particle size of the layered compound.

The content of the oxygen storage material in the composition is not particularly limited, and can be set to an effective amount that can inhibit the oxidation of the semisiloxane derivative used. Relative to the total mass of the semisiloxane derivative and the oxygen storage material, the oxygen storage material is, for example, 0.05% by mass or more, for example, 0.1% by mass or more, for example, 0.5% by mass or more, for example, 1% by mass or more, For example, it is 3% by mass or more, for example, 5% by mass or more, for example, 10% by mass or more, for example, 15% by mass or more. Relative to the same total amount, for example, it may be 25% by mass or less, or for example, 20% by mass or less. In addition, relative to the total mass of the semisiloxane derivative and the oxygen storage material, the content of the oxygen storage material can be set to, for example, 0.05% by mass or more and 50% by mass or less, and for example, 0.1% by mass or more and 40% by mass or less.

The composition may include either or both of layered compound and oxygen storage material. If both are included, the respective inherent effects will act to effectively inhibit the oxidation of the semisiloxane derivative and obtain excellent heat resistance. Even if both are contained, each may be contained within the range of the content already explained. In addition, the present composition may include both a layered compound and an oxygen storage material. The total mass of the layered compound and the oxygen storage material relative to the total mass of the semisiloxane derivative, the layered compound and the oxygen storage material 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, for example, 20% by mass or more and 60% by mass or less.

(The state of this composition) The composition system can take various forms. This composition may include, for example, an uncured (not cross-linked or polymerized by a polymerizable functional group) semi-siloxane derivative, which is a composition before film formation or molding (typically an indefinite shape such as a liquid) body).

In addition, the present composition may include, for example, a cured product of a semisiloxane derivative, a film-like or molded product formed on the surface of the object to be processed.

(Composition containing unhardened semi-siloxane derivatives) The present composition in this aspect may contain, for example, a semisiloxane derivative having an organic functional group such as a polymerizable functional group, a layered compound, and/or an oxygen storage material. Furthermore, if necessary, the initiator and/or polymerization catalyst (hardener) required for curing or polymerization may be included. This composition has uncured semisiloxane derivatives together with layered compounds and/or oxygen storage materials. When the semisiloxane derivatives are exposed to heat, they are heated and hardened, or when the hardened substance is exposed to heat. At times, the heat resistance of semisiloxane derivatives or their hardened materials has been sought. Furthermore, as other components, a solvent may be included.

(Polymerization initiator) The composition may contain a polymerization initiator for polymerizing the semisiloxane derivative through the polymerizable functional group. The type of polymerization initiator varies with the type of polymerizable functional group possessed by the semisiloxane derivative, but various initiators such as photoinitiators, thermal initiators, and radical polymerization initiators can be used. Starter or hardener. If you are a professional, you can consider the polymerizable functional group used or the purpose of the composition, and appropriately select the type or amount of polymerization initiator or curing agent. For example, as a radical polymerization initiator, well-known organic peroxides, azo compounds, etc. can be used.

Examples of organic peroxides include benzyl peroxide, laurel peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-tert-butyl peroxide, and the like. Moreover, as an azo compound, azobisisobutyronitrile, azobisisovaleronitrile, azobisisocapronitrile, etc. are mentioned.

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

(Hydrosilication catalyst) As a polymerizable functional group, when an unsaturated organic group is present in the presence of a hydrogen atom of a hydrosilyl group, it is used for curing (hydrosilication) by the hydrosilation of a semisiloxane derivative Examples of the hydrosilation catalyst include simple substances of the eighth to tenth group metals such as cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum, organometallic complexes, metal salts, and metal oxides. Generally, platinum-based catalysts are used. Examples of platinum-based catalysts include cis-PtCl ₂ (PhCN) ₂ , platinum carbon, 1,3-divinyltetramethyldisiloxane coordinated platinum complex (Pt(dvs)), platinum Vinyl methyl cyclic silicone complex, platinum carbonyl, vinyl methyl cyclic silicone complex, ginseng (dibenzylidene acetone) diplatin, chloroplatinic acid, bis(ethylene)tetrachloride Diplatinum, cyclooctadiene dichloroplatinum, bis(cyclooctadiene)platinum, bis(dimethylphenylphosphine)dichloroplatinum, tetrakis(triphenylphosphine)platinum, etc. Among these, particularly preferred are 1,3-divinyltetramethyldisiloxane coordinated platinum complexes (Pt(dvs)), platinum vinyl methyl cyclosiloxane complexes Compounds, platinum carbonyl and vinyl methyl 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 0.5-100 mass ppm, and particularly preferably 1-50 mass ppm relative to the amount of the semisiloxane derivative.

When the composition contains a catalyst for the hydrosilation reaction, the hydrosilation reaction may have priority over the dehydration polycondensation of the remaining alkoxy or hydroxyl groups in the structural unit (1-5), and one side has a hydrosilation structure. , On the one hand, it is possible to further crosslink the above-mentioned alkoxy group or hydroxyl group.

When the composition contains a hydrosilation catalyst, in order to inhibit the gelation of the semisiloxane derivative and improve the storage stability, a hydrosilation reaction inhibitor can be added. Examples of inhibitors for the hydrosilation reaction include methyl vinyl cyclotetrasiloxane, acetylenic alcohols, siloxane-modified acetylenic alcohols, hydrogen peroxide, containing nitrogen atoms, sulfur atoms, or phosphorus atoms Inhibitors of the hydrosilation reaction.

The composition may be a composition for film formation, or it may contain substantially no hydrosilation catalyst. As described later, even in the absence of a hydrosilation catalyst, the semi-siloxane derivative can be hardened by accelerating the hydrosilation reaction by heat treatment. In this composition, the so-called substantially no hydrosilation catalyst means that in addition to deliberately not adding the hydrosilation catalyst, there is also the content of the hydrosilation catalyst relative to the amount of the semisiloxane derivative For example, it is less than 0.1 mass ppm, and for example, it is 0.05 mass ppm or less.

(Solvent) Semisiloxane derivatives can also be used directly, but they can also be diluted with solvents for film formation if necessary. The solvent is preferably a solvent capable of dissolving the semi-siloxane derivative. Examples of the solvent include aromatic hydrocarbon solvents, chlorinated hydrocarbon solvents, alcohol solvents, ether solvents, amide solvents, ketone solvents, ester solvents, Various organic solvents such as Luosu solvents and aliphatic hydrocarbon solvents. In addition, in the presence of a hydrosilation catalyst such as Pt, in order to avoid decomposition of Si-H groups, a solvent other than alcohol is preferred.

(Other ingredients) Various additives can be further added when the composition is hardened. Examples of additives include reactive diluents such as tetraalkoxysilanes, trialkoxysilanes (trialkoxysilanes, trialkoxyvinylsilanes, etc.), or those that are derived from semisiloxanes. Monomers or oligomers of the same or similar polymerizable functional groups provided in the product. These additives are used in the range where the heat resistance of the obtained hardened semisiloxane derivative is not impaired.

By supplying this composition to the surface of a processed body having an arbitrary shape and curing it to form a film, a film with excellent heat resistance can be formed. For example, the composition can be supplied to the surface of the processed part, and then the composition can be hardened.

The supply system of this composition to the surface of the object to be processed is not particularly limited, and, for example, a spray method, a casting method, a spin coating method, a bar coating method, and other ordinary coating methods can be used.

(Composition of hardened substance containing semisiloxane derivatives) The composition may also be a composition containing a cured product that is cured by polymerizing a polymerizable functional group-containing semisiloxane derivative. The composition may also contain layered compounds and/or oxygen storage materials. The present composition is, for example, a composition obtained by polymerizing a semisiloxane derivative having such a functional group by heating in the presence of a layered compound and/or an oxygen storage material.

As the cured product of the semisiloxane derivative, it can be exemplified by adding the unreacted alkoxy group in the semisiloxane derivative, that is, the alkoxy group or hydroxyl group of R ⁴ in the constituent unit (1-5). Dehydration and polycondensation, fully forming siloxane bonds, and promoting cross-linking to harden (hardening caused by polycondensation of residual alkoxy groups is also called primary hardening). This cured product (hereinafter, also referred to as a primary cured product) can also be included in the semisiloxane derivative represented by the composition formula (1).

Other cured products of semisiloxane derivatives include the promotion of cross-linking by the reaction of the polymerizable functional groups of the constituent units (1-2) to (1-4), and the curing ( This hardening is also called secondary hardening). The cured product (hereinafter also referred to as a secondary cured product) may include: having at least a part of polymerizable functional groups in these structural units in the semisiloxane derivative based on the polymerizability of the functional base. Derivatives of semi-siloxane derivatives of polymerized structural part.

Other hardened products of semisiloxane derivatives can be exemplified by the generation of hydrosilation reaction between the hydrogen atoms of the structural units (1-2) to (1-4) and the unsaturated organic groups to promote It is a hardened product formed by cross-linking and hardening (this hardening is also called secondary hardening). The cured product (hereinafter also referred to as a secondary cured product) may include: a functional group (hydrosilyl group and unsaturated organic group) containing the hydrosilation reaction in these structural units from the semi-siloxane derivative The structural part (-Si-CC-Rm-Si-, -Si-C=C-Rm-Si-) of the carbon-carbon bond (single bond or double bond) of the unsaturated organic group formed by at least part of the hydrosilation reaction ) (In this specification, it is also referred to as a hydrosilation structure part; R is, for example, an organic group having 1 to 8 carbon atoms, and m is an integer of 0 or 1) derivatives of semi-siloxane derivatives.

When the present composition is formed into a film, the present composition is substantially a secondary cured product of a semisiloxane derivative. In addition to the polymerized part by the polymerizable functional group, there is a hydrosilated structure part that can contribute to the practical membrane strength or membrane performance.

The primary hardening of the semisiloxane derivative will be accompanied by secondary hardening, and the secondary hardening will be accompanied by primary hardening. However, the secondary hardening is accompanied by primary hardening in most cases. Therefore, the hardened product system of the semisiloxane derivative is generally a secondary hardened product, which is accompanied by primary hardening in most cases. A typical cured product is characterized by the presence or absence of a cross-linked structure for secondary curing. For example, the cured product can be used to detect the regularity (irregularity) of structural units or structures such as Q units, T units, D units, M units, and alkoxy groups by using ¹ H NMR and ²⁹ Si NMR, and by The characteristic base is detected by IR spectrum, and its composition or structure is defined.

In addition to the semi-siloxane derivative or its cured product, this composition system may also contain other components as needed.

(Oxidation suppression method and heat resistance method) The method for inhibiting the oxidation of a semisiloxane derivative or its cured product disclosed in this specification may include a step of heating the semisiloxane derivative or its cured product together with the layered compound and/or the oxygen storage material. The oxidation inhibition method is also the heat-resistant method of the semisiloxane derivative or its hardened substance. In the steps of producing hardened semisiloxane derivatives and the steps of heating the hardened materials in various aspects of the present composition described above, the layered compound and/or oxygen storage material suppresses the semisiloxane derivative or The oxidation of the hardened substance. Therefore, by providing such a step, the oxidation of the semisiloxane derivative or its cured product can be suppressed, and heat resistance can be achieved.

Based on the above, in accordance with this specification, it is possible to provide an oxidation inhibitor or heat resistance enhancer of a semi-siloxane derivative or a cured product thereof that uses a layered compound and/or an oxygen storage material as an active ingredient. [Example]

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

In addition, in the following description, parts and% all mean parts by mass and% by mass. [Example 1]

(Production of composition containing semisiloxane derivative and its hardened substance) Measure 70 parts of a semisiloxane derivative (manufactured by Toagosei Co., Ltd., MAC-SQ TM-100, viscosity 4000mPa·s) having a methacrylic acid group in the T unit in a vial, and talc (Japanese talc, SG95 , D50=2.5 μm) 30 parts and 0.7 parts of thermal radical initiator (Nippon Oil & Fats, Vertibull E, tertiary butylperoxy-2-ethylhexyl monocarbonate), using a rotation and revolution mixer, mixing at 1800rpm In 1 minute, the composition of Test Example 1 was obtained.

The composition of Test Example 1 was coated on a sand-blasted aluminum plate, and similarly bonded to the sand-blasted aluminum plate, heated at 120°C for 1 hour (DK63 manufactured by Yamato Gakuin Co., Ltd.), and then heated at 150°C for 1 hour , It was thermally cured to obtain a test piece of Test Example 1.

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

The measurement of the tensile shear strength of the test piece was performed using Strograph 20-C manufactured by Toyo Seiki Co., Ltd. In addition, the test piece was also subjected to measurement of tensile shear resistance during heating at 200°C. The stretching speed is set to 10 mm/min. The results are shown in Table 1.

In addition, as a control, only the semisiloxane derivative was used, and the composition was prepared in the same manner as in Test Example 1 to prepare a test piece, which was used as the test piece of Comparative Example A. In addition, a composition containing bisphenol A epoxy resin: talc (75 parts: 25 parts) was prepared. Using this composition, it was cured at 120°C for 1 hour and then at 150°C for 1 hour to obtain the test of Comparative Example B sheet. 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 combined results are shown in Table 1.

As shown in Table 1, the test piece prepared with the talc-containing semisiloxane derivative (Test Example 1) is excellent in suppressing the test piece regardless of heating at 350°C in the air for 1 hour to several hours The reduction in tensile shear strength of the resin inhibits the reduction in bonding strength. In contrast, the test piece prepared with the semi-siloxane derivative without adding talc (Comparative Example A) and the mixed composition of epoxy resin and talc (Comparative Example B) showed significant tensile shear resistance Decrease in strength. [Example 2]

(Thermal behavior of the composition containing semi-siloxane derivatives) (Preparation of semisiloxane derivative (liquid, uncured curable composition) composition) Prepared and mixed 3 kinds of 70 parts of the same semisiloxane derivative (MAC-SQ TM-100) as used in Example 1 and 30 parts of talc (Japanese talc, D50=1μm, 2.5μm and 5μm) The curable composition (liquid).

(Preparation of semisiloxane derivative (hardened substance) composition) 70 parts of semisiloxane derivative (MAC-SQ TM-100), 30 parts of talc (SG25, Japanese talc, D50=2.5μm), and 0.7 parts of thermal radical initiator (Nippon Oils and Fats, Vertibull E), and The thermosetting composition A was prepared in the same manner as in Example 1, applied on a sandblasted aluminum plate, heated at 120°C for 1 hour (manufactured by Yamato Gakuin Co., Ltd., DK63), and then heated at 150°C for 1 hour. The cured product A is obtained by thermal curing.

In addition, the same semisiloxane derivative, talc (SG95) and cerium oxide zirconia composite oxide (average particle size 5-10nm) are each mixed in a mass ratio of 7:3:1, and the thermal radicals are mixed together. The starting agent (NOF, Vertibull E) 0.7 parts, the thermosetting composition B was prepared in the same manner as in Example 1, and the thermosetting composition B was thermally cured to obtain a cured product B.

Furthermore, 0.7 parts of the same semisiloxane derivative and a radical initiator (Nippon Oil & Fats, Vertibull E) were used in the same manner as in Example 1 to prepare a comparative thermosetting composition, and applied to the sandblasted After heating the aluminum plate at 120°C for 1 hour (manufactured by Yamato Gakuin Co., Ltd., DK63), it was further heated at 150°C for 1 hour to thermally cure to obtain a control cured product.

(Evaluation of Thermal Behavior) Only 3 types of liquid composition MAC-SQ TM-100 and thermal behavior were evaluated by TGA. The result of the preparation is the composition shown in Fig. 1, and the thermal behavior of these compositions was evaluated by TGA. In addition, the thermal behavior of the cured product of bisphenol A epoxy resin was also evaluated. The results are shown in Figure 1. In addition, in Fig. 1, in addition to the actual measured value of the mass change (%) of the various compositions, the mass reduction of the semisiloxane derivative without talc is multiplied by 0.7 to make the effective half The weight change rate of the siloxane derivative is consistent with the weight change of the aforementioned composition.

TGA was used to evaluate the thermal behavior of hardened objects A, B and the control hardened objects. The results are shown in Figure 2. Figure 2(a) shows the weight change rate from 0°C to 1000°C, and in the same figure (b), the temperature range from 300°C to 600°C is enlarged to show the weight change rate.

As shown in Figure 1, it can be seen that the addition of talc indicates that the starting temperature of the oxidation of the composition containing the semisiloxane derivative (liquid, unhardened curable composition) is shifted to the high temperature side, and polymerization Reduce the temperature shift to the high temperature side that is 20°C or higher than bisphenol A epoxy resin. In addition, when the average particle size of talc is 1 to 5 μm, the high temperature side displacement of the weight reduction temperature occurs. Furthermore, for these compositions, when TGA was performed in nitrogen, there was no difference in the presence or absence of talc.

In addition, as shown in FIG. 2, regarding the cured product of the semisiloxane derivative, it can be seen that the polymerization reduction start temperature system indicating oxidation shifts to the high temperature side.

From the above, it can be seen that the improvement of heat resistance by layered compounds such as talc and/or oxygen storage materials is due to the suppression of oxidation of the semisiloxane derivative (uncured) and its cured product. Furthermore, it can be seen that in addition to talc, the addition of oxygen storage materials such as ceria-zirconia composite oxides further suppresses oxidation. [Example 3]

(Experimental examples 1-17 of hardened products of semisiloxane derivatives and layered compounds and/or oxygen storage materials) In the same manner as in Example 1, the composition and test pieces of Test Example 1 were prepared. In addition, except that the components shown in the following table were used in each part, the same operation as that of Test Example 1 of Example 1 was performed to prepare the compositions of Test Examples 1 to 17, and each test piece was prepared.

(Comparative examples 1 to 3 of only semi-siloxane derivatives or hardened products of semi-siloxane derivatives and other components) The composition of Comparative Example 1 was prepared in the same manner as in Example 1. Except for preparing a test piece and adding the components shown in the table below, the same operation as in Test Example 1 of Example 1 was performed to prepare Comparative Example 2 And 3 composition and test piece.

(Comparative examples 4 to 5 of cured epoxy resin) The same operation as that of Example 1 and Comparative Example 2 was performed to prepare the compositions and test pieces of Comparative Examples 4 and 5.

A part of these test pieces was heated at 350°C for 1 hour. In addition, some test pieces were heated at 200°C for 95 hours, 430 hours, and 1000 hours. In any case, as in Example 1, DK63 manufactured by Yamato Academy Co., Ltd. was used. In addition, some test pieces were heated at 250°C for 95 hours, 430 hours, and 1000 hours.

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

Also, the description in the following table is explained. MAC-SQ TM-100: Radical hardening type semi-siloxane derivative containing methacrylic acid group (manufactured by Toagosei Co., Ltd.) AC-SQ TA-100: Free radical hardening type semi-silicone containing acrylic acid group Oxyane derivatives (manufactured by Toagosei Co., Ltd.) Epoxy resin: Bisphenol A epoxy resin talc SG95: Talc (layered magnesium silicate compound), D50=2.5μm (manufactured by Talc Co., Ltd.) Talc SG2000: Talc (layered magnesium silicate compound), D50=1μm (manufactured by Nippon Talc Co., Ltd.) Talc P-3: Talc (layered magnesium silicate compound), D50=5μm (manufactured by Nippon Talc Co., Ltd.) ) Hexagonal boron nitride: hBN (Wako hBN), average particle size 2～3μm (manufactured by Wako Pure Chemical Industries Co., Ltd.) Ceria-zirconia composite oxide: CeO ₂ /ZrO ₂ , average particle size 5-10nm Cerium oxide 1: CeO ₂ , average particle size 5-10nm Cerium oxide 2: CeO ₂ , average particle size 5.5μm Zirconia: ZrO ₂ , average particle size 10-15nm Iron oxide: Fe ₂ O ₃ , average particle size 50nm or less Perbutyl E: tert-butylperoxy-2-ethylhexyl monocarbonate (manufactured by Nippon Oil & Fat Co., Ltd.)

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

The average particle size of cerium oxide zirconia composite oxide, cerium oxide 1, zirconia and iron oxide is analyzed by the BET method (multipoint method) and measured by the gas adsorption method using nitrogen (N ₂ ) gas as the adsorbate Calculate the average particle size from the specific surface area (m ² /g, S) obtained. In the measurement of the nitrogen adsorption capacity, each sample was degassed under vacuum at 300°C for 12 hours or more, and then gas was adsorbed at 77K. In addition, the cerium oxide 2 is measured by a laser diffraction/scattering method in the same way as talc based on the relationship of the particle size.

As shown in Table 2, the test piece (Experiment Examples 1 to 5) attached to the cured product of a semi-siloxane derivative hardened by containing only the layered compound, and the derivative hardened by containing the layered compound and oxygen storage material The test piece followed by the hardened substance (Experimental Examples 6-16) and the hardened derivative hardened with only oxygen-containing storage materials (Experimental Example 17), both before and after the temperature treatment, excellently inhibit resistance Reduction of tensile shear strength. Among them, compare the rate of change in tensile shear strength after heat treatment at 350°C for 1 hour in Test Examples 1 to 17 and Comparative Example 1, which contains other components of a cured product of semisiloxane derivatives. The same rate of change of Comparative Examples 2 to 3 of the alkane derivative hardened product and Comparative Example 4 using epoxy resin shows that the test piece of the test example using the layered compound and/or oxygen storage material is well suppressed at 350°C The lower tensile shear strength is reduced. Also, even if silicon dioxide, calcium carbonate, etc. are added, it is the same as if it is not added at all. In addition, as a mineral of a kind of layered compound, about mica and bentonite, the cured product was obtained in the same manner as in Test Example 1, and the adhesive strength was measured in the same manner. As a result, it was also confirmed that the effect of adding the layered compound was obtained.

Furthermore, according to Test Examples 6-16 containing both the layered compound and the oxygen storage material, it can be seen that the inclusion of these two is effective in suppressing (heat-resistant) the decrease in tensile shear strength after heat treatment. The effect of equal series multiply. In addition, it can be seen that even if it is kept at 350°C for 1 hour or at 200°C or 250°C for a long time, a high heat resistance effect is obtained. In addition, it can be seen that even if the polymerizable functional group is a methacryloyl group, a heat-resistant effect that is substantially equivalent to that of the acryloyl-containing semisiloxane derivative is obtained.

In addition, as for the layered compound, as shown in Test Examples 1 to 5, 3 parts of the semisiloxane derivative is used to obtain a sufficient effect with respect to 7 parts of the semisiloxane derivative. The total mass of, for example, 5% or more and 50% or less, preferably 10% or more and 40% or less, more preferably in the range of 20% or more and 40% or less, so that the heat-resistant effect can be exerted. Regarding the oxygen storage material, as shown in Test Examples 6-17, relative to the total mass of the semisiloxane derivative and the oxygen storage material, the oxygen storage material is effective if it is 0.007% or more, and if it is 0.4% or more. It is more effective, and it is more effective if it is more than 10%, and it is particularly effective if it is more than 20%. Also, even if the addition amount is 30%, sufficient adhesive strength is shown. Based on the above, it can be seen that the oxygen storage material can be set to 0.07% or more and 30% or less, preferably 0.4% or more and 20% or less, relative to the total mass of the semisiloxane derivative and the oxygen storage material. In addition, when the layered compound and the oxygen storage material are contained, it can be seen that even if it exceeds 40% of the total mass of the semisiloxane derivative, the layered compound and the oxygen storage material, sufficient adhesive strength can be maintained.

In addition, although the oxygen storage material exhibits a heat-resistant effect on the cured semi-siloxane derivative, the epoxy resin does not sufficiently exhibit a heat-resistant effect.

Based on the above, we can see the effect of layered compounds and oxygen storage materials. It acts more effectively on semisiloxane derivatives or their hardened products.

In addition, although both talc and hexagonal boron nitride of the layered compound exert an excellent heat-resistant effect, it can be seen that the heat-resistant effect is greater when the average particle size is small. That is, if the average particle diameter exceeds 5 μm, the heat-resistant effect tends to vary. Therefore, it can be seen that the layered compound preferably has an average particle diameter of less than 5 μm, preferably 4 μm or less, and more preferably 3 μm or less.

In addition, it can be seen that the oxygen storage materials of Examples 1 to 5 and Comparative Example 1 exert a higher heat resistance effect. Among the oxygen storage materials, it can be seen that the ceria-zirconia composite oxide system with high oxygen storage capacity also has the highest oxidation resistance. In addition, in oxygen storage materials, if the average particle size exceeds 5 μm, the antioxidant effect tends to decrease. It can be seen that the average particle size of the oxygen storage material is preferably less than 5 μm, more preferably 4 μm or less, and particularly preferably 3 μm Hereinafter, it is more preferably 2 μm or less, and particularly preferably 1 μm or less. [Example 4]

(Thermal behavior of the composition of the cured product of other semisiloxane derivatives) As a semisiloxane derivative, the following semisiloxane derivative (OX-SQ) with oxetanyl group in the SiO _1.5 unit , TX-100, manufactured by Toagosei Co., Ltd., hereinafter referred to as semisiloxane A) and similarly the following semisiloxane derivatives with epoxy groups in SiO _1.5 units (Toagosei Co., Ltd., Hereinafter referred to as semisiloxane B), talc (SG95) and ceria-zirconia composite oxide (average particle size 5-10nm) are used, and each is mixed at a mass ratio of 7:3:1 to prepare a composition (liquid ), for these compositions, the thermal behavior is evaluated by TGA. In addition, TGA is similarly performed for only semisiloxanes A and B. The results are shown in Figure 3. Furthermore, in Fig. 3, based on the actual measured value of the mass change (%) of semisiloxane A and B, the mass change is multiplied by 0.63, which shows that the presence of talc in the aforementioned composition has been offset The respective mass changes of semisiloxane A and B.

As shown in FIG. 3, it can be seen that by adding talc and ceria-zirconia composite oxide, the starting temperature of the weight reduction indicating the hardening of the hemisiloxane derivative is shifted to the high temperature side.

From the above, it can be seen that the layered compound and the oxygen storage material system achieve the same oxidation inhibitory effect and heat-resistant effect even in the semi-siloxane cured product having such a polymerizable functional group.

[Figure 1] A graph showing the thermal behavior of a methacryloyl-based semi-siloxane derivative. [Figure 2] A diagram showing the thermal behavior of the cured product of a semi-siloxane derivative. [Figure 3] A graph showing the thermal behavior of a semisiloxane derivative with oxetanyl and epoxy groups.

Claims (17)

A semi-siloxane derivative composition, which contains: Semisiloxane derivatives, and Layered compound. The composition of claim 1, wherein the layered compound is one or more selected from the group consisting of talc and boron nitride. Like the composition of 1 or 2, wherein the aforementioned layered compound is talc. The composition according to any one of claims 1 to 3, wherein the average particle diameter of the layered compound is 5 μm or less. 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 to 50% by mass relative to the total mass of the semisiloxane derivative and the layered compound. The composition described in any one of claims 1 to 5, which further contains an oxygen storage material. A semi-siloxane derivative composition, which contains: Semisiloxane derivatives, and Oxygen storage material. The composition of 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 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 to 40% by mass relative to the total mass of the semisiloxane derivative and the oxygen storage material. The composition according to any one of claims 1 to 10, wherein the semisiloxane derivative has a polymerizable functional group. A sclerosing semisiloxane derivative composition, which has: Semi-siloxane derivatives with polymerizable functional groups, and Layered compounds and/or oxygen storage materials. A hardened semi-siloxane derivative composition, which has: Cured products of semi-siloxane derivatives with polymerizable functional groups, and Layered compounds and/or oxygen storage materials. A method for inhibiting the oxidation of a semisiloxane derivative or its hardened product, which includes a step of heating the semisiloxane derivative together with a layered compound and/or an oxygen storage material. A heat-resistant method of a semisiloxane derivative or its hardened substance, which includes a step of heating the semisiloxane derivative together with a layered compound and/or an oxygen storage material. An oxidation inhibitor of a semisiloxane derivative or its hardened substance, which uses layered compounds and/or oxygen storage materials as effective ingredients. A heat resistance enhancer of a semisiloxane derivative or its hardened substance, which uses layered compounds and/or oxygen storage materials as effective ingredients.

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