WO2020080081A1 - Composition de dérivé de silsesquioxane et son utilisation - Google Patents

Composition de dérivé de silsesquioxane et son utilisation Download PDF

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WO2020080081A1
WO2020080081A1 PCT/JP2019/038571 JP2019038571W WO2020080081A1 WO 2020080081 A1 WO2020080081 A1 WO 2020080081A1 JP 2019038571 W JP2019038571 W JP 2019038571W WO 2020080081 A1 WO2020080081 A1 WO 2020080081A1
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silsesquioxane derivative
oxygen storage
storage material
layered compound
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PCT/JP2019/038571
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Japanese (ja)
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賢明 岩瀬
武士 藤田
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東亞合成株式会社
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Priority to JP2020553021A priority Critical patent/JP7276348B2/ja
Priority to CN201980068688.8A priority patent/CN112888715B/zh
Priority to KR1020217012966A priority patent/KR102640556B1/ko
Publication of WO2020080081A1 publication Critical patent/WO2020080081A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/014—Stabilisers against oxidation, heat, light or ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • the present specification relates to a composition containing a silsesquioxane derivative and its use.
  • 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 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 contains a silsesquioxane derivative and a layered compound and / or an oxygen storage material. .
  • silsesquioxane is a polysiloxane having a main chain skeleton made of Si—O bonds and having (RSiO 1.5 ) units.
  • 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).
  • 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.
  • 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).
  • w is a positive number.
  • w and x are positive numbers, and v, y, and z are 0 or positive numbers.
  • the silsesquioxane derivative may be composed of only the structural unit (1-2) (w is positive and the others are 0).
  • 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.
  • 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.
  • 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.
  • 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.
  • R 5 represents a hydrogen atom or a methyl group
  • 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.
  • R 7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • 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 ⁇ -glycidoxyethyl, ⁇ -glycidoxypropyl, ⁇ -glycidoxybutyl.
  • 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.
  • 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.
  • 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.
  • 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.
  • hydroxyl-protecting group of the protected hydroxyl group a known hydroxyl-protecting group can be used without particular limitation.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • WO 2005/010077 WO 2009/066608, 2013/099909
  • JP2011-052170A JP2013-147659A.
  • 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).
  • Q monomer silicon compound having four siloxane bond-forming groups
  • T monomer 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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
  • R 10 , R 11 and R 13 are each an alkyl group, a cycloalkyl group or aryl
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • the siloxane bond-forming group contained in the M monomer is an alkoxy group or a siloxy group. It is preferable.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the polymerization catalyst such as water and an acid dissolved in water can be efficiently distilled off.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m or less, for example. This is because when it is 10 ⁇ m or less, good oxidation resistance is obtained. More preferably, it is 5 ⁇ m or less. Further, it is more preferably 3 ⁇ m or less, and further preferably 2.5 ⁇ m or less.
  • the lower limit is not particularly limited, but is, for example, 0.5 ⁇ m or more, and is 1.0 ⁇ m or more.
  • the average particle size of the layered compound can be measured by a laser diffraction / scattering method.
  • 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.
  • 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.
  • 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 ⁇ m or less, for example. It is considered that when the thickness is 5 ⁇ m or less, a high oxygen storage capacity is exhibited due to the surface area. More preferably, it is 1 ⁇ m 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.
  • 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 ⁇ m. 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.
  • the sample degassed under vacuum at 300 ° C. for 12 hours or more is gas adsorbed at 77K.
  • the average particle diameter is 1 ⁇ m 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.
  • both 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.
  • 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.
  • 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 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.
  • 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.
  • a solvent can be included as another component.
  • organic peroxides examples 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.
  • the hydrosilylation catalyst used for curing the silsesquioxane derivative by 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.
  • platinum complexes Pt (dvs) coordinated with 1,3-divinyltetramethyldisiloxane
  • platinum vinylmethyl cyclic siloxane complexes platinum carbonyl-vinylmethyl cyclic siloxane complexes.
  • 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.
  • the hydrosilylation reaction may take precedence over the dehydration polycondensation of the residual alkoxy group or hydroxyl group in the structural unit (1-5).
  • the above-mentioned alkoxy group or hydroxyl group is provided so as to allow further crosslinking reaction.
  • hydrosilylation reaction inhibitor 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.
  • 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.
  • the silsesquioxane derivative can be cured by promoting the hydrosilylation reaction by heat treatment even in the absence of a hydrosilylation catalyst.
  • 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.
  • 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.
  • a hydrosilylation catalyst such as Pt
  • a solvent other than alcohol is preferable in order to avoid decomposition of the Si-H group.
  • additives may be further added to the composition before it is subjected to curing.
  • 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.
  • composition can be supplied to the surface of a workpiece having an arbitrary shape and curing the composition to form a film.
  • 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.
  • 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.
  • 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.
  • a cured product hereinafter, also referred to as a primary cured product
  • 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 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.
  • the composition When the composition is formed into a film, the composition is generally a secondary cured product of a silsesquioxane derivative.
  • the hydrosilylated structure portion can contribute to practical membrane strength and membrane performance.
  • the composition contains only the silsesquioxane derivative or a cured product thereof, and may contain other components as necessary.
  • 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.
  • 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.
  • 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.
  • both parts and% represent parts by mass and% by mass.
  • Test Example 1 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.
  • 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.
  • 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.
  • test piece prepared from the silsesquioxane derivative containing talc 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.
  • 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.
  • silsesquioxane derivative liquid, uncured curable composition
  • MAC-SQ TM-100 silsesquioxane derivative
  • 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.
  • Example 2 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.
  • a radical initiator Nippon Oil and Fats, Virtuable E
  • FIG. 2 (a) shows the rate of weight change from 0 ° C. to 1000 ° C.
  • FIG. 2 (b) shows the rate of weight change by expanding the temperature range from 300 ° C. to 600 ° C.
  • 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 ⁇ m, 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.
  • 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.
  • test pieces were 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.
  • 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.)
  • 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.
  • SALD200 manufactured by Shimadzu Corporation
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m, 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 ⁇ m, preferably 4 ⁇ m or less, and more preferably 3 ⁇ m or less.
  • 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 ⁇ m, the oxidation resistance tends to decrease, and the average particle size of the oxygen storage material is preferably less than 5 ⁇ m, more preferably 4 ⁇ m or less, It has been found that the thickness is more preferably 3 ⁇ m or less, still more preferably 2 ⁇ m or less, and further preferably 1 ⁇ m or less.
  • silsesquioxane A 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.
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Afin d'améliorer la résistance à la chaleur d'un dérivé de silsesquioxane, la présente invention concerne une composition de dérivé de silsesquioxane qui contient un dérivé de silsesquioxane et un composé en couches.
PCT/JP2019/038571 2018-10-18 2019-09-30 Composition de dérivé de silsesquioxane et son utilisation WO2020080081A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114426785A (zh) * 2020-10-29 2022-05-03 阪田油墨股份有限公司 活性能量射线固化型组合物
WO2022168804A1 (fr) * 2021-02-05 2022-08-11 東亞合成株式会社 Composition d'agent de sous-couche pour stratification de couche de substance inorganique, son produit durci et son procédé de production

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004002653A (ja) * 2002-04-22 2004-01-08 Shin Kobe Electric Mach Co Ltd プリント基板用プリプレグ及びその製造法とプリント基板
JP2009256662A (ja) * 2008-03-26 2009-11-05 Nagase Chemtex Corp シルセスキオキサン誘導体及びその製造方法
JP2011148784A (ja) * 2009-12-24 2011-08-04 Dow Corning Toray Co Ltd 化粧料用粉体表面処理剤、及び、当該化粧料用粉体表面処理剤によって表面処理された粉体を含む化粧料
JP2015010151A (ja) * 2013-06-28 2015-01-19 チェイル インダストリーズ インコーポレイテッド 樹脂膜、樹脂膜の製造方法、及び塗工液
WO2015072540A1 (fr) * 2013-11-15 2015-05-21 株式会社コーセー Poudre traitée en surface obtenue en utilisant de la théanine, et préparation cosmétique la contenant
CN106739277A (zh) * 2016-11-16 2017-05-31 苏州大学 带有磁控溅射类金刚石碳膜的金属型材的制备方法与应用
CN107722828A (zh) * 2017-09-29 2018-02-23 广东冠能电力科技发展有限公司 电抗器专用防污湿涂料及其制造方法

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7297731B2 (en) * 2003-03-11 2007-11-20 3M Innovative Properties Company Coating dispersions for optical fibers
KR101054569B1 (ko) 2003-07-29 2011-08-04 도아고세이가부시키가이샤 규소 함유 고분자 화합물 및 그의 제조 방법 및 내열성수지 조성물 및 내열성 피막
US20100304152A1 (en) * 2007-10-22 2010-12-02 Flexible Ceramics , Inc. Fire resistant flexible ceramic resin blend and composite products formed therefrom
WO2009066608A1 (fr) 2007-11-19 2009-05-28 Toagosei Co., Ltd. Polysiloxane, son procédé de fabrication et procédé de fabrication d'un produit durci de celui-ci
WO2010131258A1 (fr) * 2009-05-12 2010-11-18 Council Of Scientific & Industrial Research Nanocomposite d'argile formant une microcapsule utile pour une encapsulation hôte et procédé pour celui-ci
US20120153342A1 (en) * 2010-06-08 2012-06-21 Takashi Nishimura Die-bonding material for optical semiconductor devices and optical semiconductor device using same
DE102010041676A1 (de) * 2010-09-29 2012-03-29 Wacker Chemie Ag Vernetzbare Organopolysiloxanzusammensetzung
US20150098973A1 (en) * 2012-05-09 2015-04-09 Dow Corning Corporation Composition for application to the skin comprising silsesquioxane resin wax and solid particulate
EP2878638B1 (fr) * 2012-07-27 2019-05-22 LG Chem, Ltd. Composition durcissante
JP6021605B2 (ja) * 2012-11-19 2016-11-09 新日鉄住金化学株式会社 かご型シルセスキオキサン化合物、それを用いた硬化性樹脂組成物及び樹脂硬化物
CN103305036B (zh) * 2013-06-18 2016-09-14 武汉绿凯科技有限公司 一种含poss减反射膜镀膜液及其制备方法与应用
WO2015079677A1 (fr) * 2013-11-29 2015-06-04 東レ・ダウコーニング株式会社 Matériau optique
JP6849596B2 (ja) * 2014-12-30 2021-03-24 株式会社ブリヂストン 末端官能性ポリマー及び関連する方法
WO2017038943A1 (fr) * 2015-09-02 2017-03-09 日産化学工業株式会社 Composition polymérisable comprenant un composé de silsesquioxane ayant un groupe acrylique
KR102453363B1 (ko) * 2015-09-30 2022-10-07 (주)아모레퍼시픽 묻어남이 개선된 메이크업 조성물 및 이의 제조 방법
CN105176296B (zh) * 2015-10-12 2017-12-08 中国科学院宁波材料技术与工程研究所 基于聚倍半硅氧烷改性的耐高温涂料及其应用
CN108699340A (zh) * 2016-03-02 2018-10-23 捷恩智株式会社 放热构件用组合物、放热构件、电子机器及放热构件的制造方法
CN106519701A (zh) * 2016-10-21 2017-03-22 沈阳化工大学 一种带有乙苯基氢基笼型倍半硅氧烷耐热硅橡胶制备方法
JP7069449B2 (ja) 2016-12-16 2022-05-18 株式会社ダイセル 硬化性組成物、接着シート、硬化物、積層物、及び装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004002653A (ja) * 2002-04-22 2004-01-08 Shin Kobe Electric Mach Co Ltd プリント基板用プリプレグ及びその製造法とプリント基板
JP2009256662A (ja) * 2008-03-26 2009-11-05 Nagase Chemtex Corp シルセスキオキサン誘導体及びその製造方法
JP2011148784A (ja) * 2009-12-24 2011-08-04 Dow Corning Toray Co Ltd 化粧料用粉体表面処理剤、及び、当該化粧料用粉体表面処理剤によって表面処理された粉体を含む化粧料
JP2015010151A (ja) * 2013-06-28 2015-01-19 チェイル インダストリーズ インコーポレイテッド 樹脂膜、樹脂膜の製造方法、及び塗工液
WO2015072540A1 (fr) * 2013-11-15 2015-05-21 株式会社コーセー Poudre traitée en surface obtenue en utilisant de la théanine, et préparation cosmétique la contenant
CN106739277A (zh) * 2016-11-16 2017-05-31 苏州大学 带有磁控溅射类金刚石碳膜的金属型材的制备方法与应用
CN107722828A (zh) * 2017-09-29 2018-02-23 广东冠能电力科技发展有限公司 电抗器专用防污湿涂料及其制造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114426785A (zh) * 2020-10-29 2022-05-03 阪田油墨股份有限公司 活性能量射线固化型组合物
WO2022168804A1 (fr) * 2021-02-05 2022-08-11 東亞合成株式会社 Composition d'agent de sous-couche pour stratification de couche de substance inorganique, son produit durci et son procédé de production
CN116897195A (zh) * 2021-02-05 2023-10-17 东亚合成株式会社 无机物质层层叠用底涂层剂组合物、其固化物及其制造方法

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