Polysilsesquioxane composition and cured product

Abstract

The present invention provides a curable composition that can yield a cured product having excellent resistance to thermal decomposition and adhesiveness to a metal substrate. The present invention provides a polysilsesquioxane composition comprising a polysilsesquioxane and at least one compound selected from the group consisting of phosphorus-containing compounds, triazinethiol compounds, hydroxyl group-containing compounds having a boiling point of 230°C or higher, and carboxy group-containing compounds having a boiling point of 230°C or higher, wherein the phosphorus-containing compound is at least one compound selected from the group consisting of phosphine compounds, phosphate compounds, phosphinate compounds, and phosphonate compounds.

Description

[Technical field]

[0001] The present invention relates to a polysilsesquioxane composition. More specifically, the present invention relates to a polysilsesquioxane composition capable of giving a cured product having excellent resistance to thermal decomposition and adhesion to metal substrates, and the cured product thereof. [Background technology]

[0002] Silicon-based compounds such as polysilsesquioxanes can be endowed with a variety of properties due to their organic functional groups and the physical properties of ceramics, and are therefore widely used as raw materials for various industrial products in the fields of electronics, optoelectronic devices, displays, and the like.

[0003] Various studies have been conducted on curable compositions containing silicon compounds. For example, Patent Document 1 discloses a composition containing a silicon-based compound containing an alkyl group and an aryl group, a thermally activated condensation catalyst, and a solvent. Furthermore, Patent Document 2 describes a crosslinkable composition that includes a first silicon-containing resin containing an alkyl group and an aryl group and having a weight average molecular weight of 1,000 AMU to 10,000 AMU, a second silicon-containing resin containing an aryl group and having a weight average molecular weight of 900 AMU to 5,000 AMU, a solvent, and a thermally activated catalyst. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2014-208838 A [Patent Document 2] Special Publication No. 2018-516998 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the thermal decomposition temperature of the conventional curable composition containing silicon-based compounds is not sufficiently high, and the thermal decomposition resistance may be insufficient depending on the application.In addition, the obtained cured product has a problem that the adhesion to the substrate, especially the metal substrate, is low.Therefore, in order to make the above-mentioned curable composition usable in a wider variety of applications, it is necessary to improve the thermal decomposition resistance and the adhesion to the metal substrate.

[0006] The present invention has been made in consideration of the above-mentioned current situation, and an object of the present invention is to provide a curable composition that can give a cured product that has excellent resistance to thermal decomposition and adhesion to metal substrates. [Means for solving the problem]

[0007] The present inventors have conducted various studies on compositions containing polysilsesquioxanes, and have found that by containing polysilsesquioxanes and a specific compound, the specific compound acts as a catalyst and also acts as a heat resistance improver, increasing the thermal decomposition temperature of the resulting cured product and improving thermal decomposition resistance. The present inventors have also found that the cured product obtained from such a composition has excellent adhesion, particularly to metal substrates, and have completed the present invention.

[0008] That is, the present invention relates to a polysilsesquioxane composition comprising a polysilsesquioxane and at least one compound selected from the group consisting of a phosphorus-containing compound, a triazine thiol compound, a hydroxyl group-containing compound having a boiling point of 230° C. or higher, and a carboxy group-containing compound having a boiling point of 230° C. or higher, wherein the phosphorus-containing compound is at least one compound selected from the group consisting of a phosphine compound, a phosphate compound, a phosphinate compound, and a phosphonate compound.

[0009] The polysilsesquioxane is preferably a compound containing a basic skeleton represented by the following general formula (1). [R 1 SiO 1.5 ] n (1) (In the formula, R 1 represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or a vinyl skeleton-containing group. The alkyl group having 1 to 10 carbon atoms and the aryl group may have a substituent. n R 1 may be the same or different.)

[0010] The polysilsesquioxane is represented by the general formula (1) R 1 As the alkyl group, it is preferable that the alkyl group has 1 to 10 carbon atoms and an aryl group.

[0011] The polysilsesquioxane is represented by the general formula (1) R 1 As the alkyl group, it is preferable that the alkyl group has 3 to 10 carbon atoms and that the aryl group has 3 to 10 carbon atoms.

[0012] The polysilsesquioxane is represented by the general formula (1) R 1 As the alkyl group, it is preferable that the alkyl group has a methyl group, an alkyl group having 3 to 10 carbon atoms, or an aryl group.

[0013] The polysilsesquioxane is represented by the general formula (1) R 1 As the alkyl group, it is preferable that the alkyl group has 3 to 10 carbon atoms, an aryl group, or a vinyl skeleton-containing group.

[0014] The carbon amount of the alkyl group having 3 to 10 carbon atoms is preferably 3 mass % or more of the total carbon amount of the polysilsesquioxane.

[0015] The polysilsesquioxane preferably contains structural units represented by the following general formula (1') in an amount of 40 mol % or more relative to 100 mol % of all structural units of the polysilsesquioxane. [R 1 SiO 1.5 ] (1') (In the formula, R 1 represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or a group containing a vinyl skeleton. The alkyl group having 1 to 10 carbon atoms and the aryl group may have a substituent.

[0016] The polysilsesquioxane preferably further contains a basic skeleton represented by the following general formula (2). [R 2 R 3 SiO 1.0 ] m (2) (In the formula, R 2 and R 3 are the same or different and each represents an alkyl group having 1 to 10 carbon atoms, an aryl group, a vinyl skeleton-containing group, or -OR 4 The alkyl group having 1 to 10 carbon atoms and the aryl group may have a substituent. R 4 represents a hydrogen atom, an alkyl group, an aryl group, or an acetyl group. 2 and R 3 may be the same or different.)

[0017] The above phosphine compound preferably has a boiling point of 100° C. or higher.

[0018] The polysilsesquioxane composition preferably further contains a hindered phenol-based antioxidant.

[0019] The polysilsesquioxane composition is preferably used for optical materials.

[0020] The polysilsesquioxane composition is preferably for use as a low dielectric material.

[0021] The present invention also relates to a cured product obtained by curing the above-mentioned polysilsesquioxane composition. Effect of the Invention

[0022] The polysilsesquioxane composition of the present invention can provide a cured product having excellent thermal decomposition resistance and adhesion to metal substrates. The polysilsesquioxane composition of the present invention is suitable for use in various applications such as electric / electronic parts, optical parts, and display devices. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] The present invention will be described in detail below. In addition, a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[0024] 1. Polysilsesquioxane Composition The present invention relates to a polysilsesquioxane composition comprising a polysilsesquioxane and at least one compound selected from the group consisting of a phosphorus-containing compound, a triazine thiol compound, a hydroxyl group-containing compound having a boiling point of 230° C. or higher, and a carboxy group-containing compound having a boiling point of 230° C. or higher, wherein the phosphorus-containing compound is at least one selected from the group consisting of a phosphine compound, a phosphate compound, a phosphinate compound, and a phosphonate compound. The polysilsesquioxane composition of the present invention can provide a cured product having excellent thermal decomposition resistance and adhesion to a metal substrate.

[0025] It is presumed that the reason why the polysilsesquioxane composition of the present invention can give a cured product having excellent thermal decomposition resistance and adhesion to metal substrates is that at least one compound selected from the group consisting of phosphorus-containing compounds, triazine thiol compounds, hydroxyl group-containing compounds having a boiling point of 230°C or higher, and carboxy group-containing compounds having a boiling point of 230°C or higher serves as a heat resistance improver, thereby improving the thermal decomposition resistance of the cured product of the polysilsesquioxane composition, and that the adhesion between the resin and metal substrates is improved due to the interaction via the above compound.

[0026] Each component contained in the polysilsesquioxane composition of the present invention will be described. <Polysilsesquioxane> Polysilsesquioxanes are compounds containing siloxane bonds (Si-O-Si) obtained by hydrolysis and condensation of trifunctional organoalkoxysilanes.

[0027] The polysilsesquioxane preferably contains a basic skeleton represented by the following general formula (1). [R 1 SiO 1.5 ] n (1) (In the formula, R 1 represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or a vinyl skeleton-containing group. The alkyl group having 1 to 10 carbon atoms and the aryl group may have a substituent. n R 1 may be the same or different.) The basic skeleton represented by the above general formula (1) is composed of a structural unit containing a silicon atom bonded to three oxygen atoms (T-structure). By including such a polysilsesquioxane, compatibility with the specific compound described below is improved, and the transparency of the obtained cured product can be improved.

[0028] In the above general formula (1), R 1 represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or a vinyl skeleton-containing group.

[0029] The alkyl group having 1 to 10 carbon atoms may be linear or branched, but is preferably linear in that it can improve flexibility.

[0030] The alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 3 to 10 carbon atoms, since it can further improve the flexibility of the cured product. The flexibility of the cured product is expressed by having a soft unit of an alkyl group having 3 to 10 carbon atoms. If the number of carbon atoms in the alkyl group exceeds 10, the surface hardness of the cured product may be reduced. The alkyl group is more preferably an alkyl group having 3 to 8 carbon atoms, and even more preferably an alkyl group having 3 to 6 carbon atoms. Note that the number of carbon atoms referred to here is the number of carbon atoms in the alkyl group, not including the number of carbon atoms in the substituent.

[0031] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a sec-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a heptyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 2,2-dimethylpentyl group, a 2,3-dimethylpentyl group, a 2,4-dimethylpentyl group, a 3-ethylpentyl group, a 2,2-dimethylpentyl group, a 2,3-dimethylpentyl group, a 2,4-dimethylpentyl group, a 3-ethylpentyl group, a 2,3-ethylpentyl group, a 2,4-dimethyl ... Examples of such alkyl groups include 2,2,3-trimethylbutyl group, n-octyl group, methylheptyl group, dimethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, trimethylpentyl group, 3-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2,2,3,3-tetramethylbutyl group, n-nonyl group, methyloctyl group, 3,7-dimethyloctyl group, dimethylheptyl group, 3-ethylheptyl group, 4-ethylheptyl group, trimethylhexyl group, 3,3-diethylpentyl group, and n-decyl group.

[0032] Among these, in terms of industrial availability, the alkyl group is preferably at least one selected from the group consisting of an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-hexyl group, an n-octyl group, and an n-decyl group, and in terms of achieving a good balance between surface hardness and flexibility of the cured product, an n-propyl group, an n-butyl group, or an isobutyl group is more preferable, and an n-propyl group is even more preferable.

[0033] Examples of the aryl group include a phenyl group, a styryl group, a tolyl group, a xylyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, and an anthracenyl group. Among these, in terms of improving solubility in organic solvents, the aryl group is preferably a phenyl group, a styryl group, a tolyl group, or a xylyl group, more preferably a phenyl group or a styryl group, and even more preferably a phenyl group.

[0034] The alkyl group and the aryl group may have a substituent, for example, an alkyl group, an aryl group, an alkenyl group, etc. The alkyl group and aryl group include the same groups as those mentioned above. Examples of the alkenyl group include a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group. The substituent preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms. The alkyl group and aryl group having 1 to 10 carbon atoms may have only one type of the above-mentioned substituent, or may have two or more types.

[0035] The vinyl skeleton-containing group is defined as "CH2=C(R a )-" (R a represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) The polysilsesquioxane includes the vinyl skeleton-containing group, and thus can provide a cured product having excellent toughness and solvent resistance. Examples of the vinyl skeleton-containing group include CH2=C(R a )-(X) m -(R a is the same as above. X represents a divalent organic group. m represents the number 0 or 1. R a is preferably a hydrogen atom or a methyl group.

[0036] The divalent organic group represented by X includes a divalent hydrocarbon group; a linking group such as -CO-, -COO-, -NH2-, -S-, or -C6H4-; and a combination thereof.

[0037] Specific examples of the vinyl skeleton-containing group include vinyl, acryloyl, methacryloyl, and allyl groups. Among these, vinyl, acryloyl, and methacryloyl groups are preferred in terms of industrial availability, and vinyl groups are more preferred in terms of resistance to hydrolysis.

[0038] The polysilsesquioxane is represented by the general formula (1) R 1 As the alkyl group, the alkyl group may have a plurality of the above-mentioned alkyl groups having 1 to 10 carbon atoms, aryl groups, and / or vinyl skeleton-containing groups. That is, the polysilsesquioxane is R 1 is an alkyl group having 1 to 10 carbon atoms, and R 1 is an aryl group, and R 1 may be a compound containing at least two kinds of skeletons each of which is a vinyl skeleton-containing group. Among these, the polysilsesquioxane is preferably a polysilsesquioxane having R 1 As the alkyl group, it is preferable that the alkyl group has 1 to 10 carbon atoms and an aryl group. In addition, the polysilsesquioxane can improve the surface hardness and flexibility of the cured product by the above-mentioned formula (1), R 1 As the alkyl group, it is preferable that the alkyl group has 3 to 10 carbon atoms and an aryl group. In addition, the polysilsesquioxane is advantageous in that it can improve the surface hardness, flexibility, and toughness of the cured product. 1 As the alkyl group, it is preferable that the alkyl group has a methyl group, an alkyl group having 3 to 10 carbon atoms, or an aryl group. In addition, the polysilsesquioxane can improve the toughness and solvent resistance of the cured product by using the R 1 As the alkyl group, it is preferable that the alkyl group has 3 to 10 carbon atoms, an aryl group, or a vinyl skeleton-containing group.

[0039] The alkyl group having 3 to 10 carbon atoms is preferably at least one selected from the group consisting of an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-hexyl group, an n-octyl group, and an n-decyl group, in terms of industrial availability.

[0040] The alkyl group preferably has a carbon content of 3% by mass or more of the total carbon content of the polysilsesquioxane. When the carbon content of the alkyl group is within the above range, it is easy to suppress cracks in the cured product. In terms of improving flexibility, the carbon content of the alkyl group is more preferably 10% by mass or more of the total carbon content of the polysilsesquioxane, and even more preferably 15% by mass or more. The upper limit of the carbon number of the alkyl group is not particularly limited, but is preferably 90% by mass or less, and more preferably 70% by mass or less, in terms of achieving both surface hardness and flexibility of the cured product. When the carbon amount of the alkyl group is within the above range, the alkyl group is particularly preferably an alkyl group having 3 to 10 carbon atoms.

[0041] In the above general formula (1), n ​​is an arbitrary integer of 1 or more. 1 may be the same or different. 1 may contain two or more different groups. That is, the polysilsesquioxane may contain two or more different groups. 1 The compound may contain two or more different groups as the substituent.

[0042] The polysilsesquioxane preferably contains 40 mol % or more, more preferably 50 mol % or more, and even more preferably 60 mol % or more of the basic skeleton represented by the general formula (1) in 100 mol % of the polysilsesquioxane. The structure of the polysilsesquioxane and the amount of the basic skeleton are as follows: 29 It can be determined by Si-NMR.

[0043] The basic skeleton represented by the above general formula (1) is composed of structural units represented by the following general formula (1'). [R 1 SiO 1.5 ] (1') (In the formula, R 1 is R in the above general formula (1). 1 is the same as

[0044] The polysilsesquioxane preferably contains the structural unit represented by the general formula (1') in an amount of 40 mol % or more relative to 100 mol % of all structural units of the polysilsesquioxane. Polysilsesquioxane is a compound composed of structural units consisting of silicon and atoms bonded to the silicon. The polysilsesquioxane preferably contains 40 mol % or more of the structural units represented by the general formula (1') relative to 100 mol % of the total amount of such silicon-centered structural units. The polysilsesquioxane more preferably contains 50 mol % or more, and even more preferably 60 mol % or more, of the structural units represented by the general formula (1') above, based on 100 mol % of all structural units of the polysilsesquioxane. The upper limit of the content of the structural unit represented by the above general formula (1') is not particularly limited, but is preferably 90 mol % or less, and more preferably 80 mol % or less, relative to 100 mol % of all structural units of the polysilsesquioxane. The structure of the polysilsesquioxane and the amount of the structural units are 29 It can be determined by Si-NMR.

[0045] The polysilsesquioxane may be a compound consisting of only the basic skeleton represented by the general formula (1) (also referred to as a homo-condensation polymer), or may be a compound containing the basic skeleton represented by the general formula (1) and another basic skeleton (containing another structural unit) other than the basic skeleton represented by the general formula (1) (also referred to as a co-condensation polymer). The above-mentioned co-condensation polymer may be, for example, a structure in which a basic skeleton represented by the above general formula (1) where n is 1 (i.e., a structural unit represented by the above general formula (1')) is alternately linked with other structural units (alternating co-condensation polymer), or a structure in which a basic skeleton represented by the above general formula (1) where n is 2 or more is alternately or randomly linked with other basic skeletons (including other structural units). The other basic skeletons include the basic skeleton represented by the general formula (2) described later, the basic skeleton represented by the formula [R 5 R 6 R 7 SiO 0.5 ] p (R 5 , R 6 , R 7 and p are as described below.) and the other structural units include a structural unit represented by the general formula (2') described below, 5 R 6 R 7 SiO 0.5 ](R 5 , R 6 and R 7 As described later, structural units represented by the following formula (I) are included.

[0046] The polysilsesquioxane preferably further contains a basic skeleton represented by the following general formula (2). [R 2 R 3 SiO 1.0 ] m (2) (In the formula, R 2 and R 3 are the same or different and each represents an alkyl group having 1 to 10 carbon atoms, an aryl group, a vinyl skeleton-containing group, or -OR 4 The alkyl group having 1 to 10 carbon atoms and the aryl group may have a substituent. 4 represents a hydrogen atom, an alkyl group, an aryl group, or an acetyl group. 2 and R 3 may be the same or different.) The basic skeleton represented by the above general formula (2) is composed of a structural unit (D-structure) containing a silicon atom bonded to two oxygen atoms.

[0047] Above R 2 and R 3 Examples of the alkyl group, aryl group, and vinyl skeleton-containing group having 1 to 10 carbon atoms represented by the formula (1) include R 1 Preferred examples of the alkyl group having 1 to 10 carbon atoms, the aryl group, and the vinyl skeleton-containing group represented by the above formula are given below. 2 and R 3 are the same or different and are preferably an alkyl group having 1 to 10 carbon atoms or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 2 carbon atoms. The substituent that the alkyl group having 1 to 10 carbon atoms and the aryl group may have is, for example, R 1 Preferred examples of the substituent include the same groups as those of the substituents of the above.

[0048] Above R 4 The alkyl group and aryl group represented by the above R 1 Preferred examples of the alkyl group and aryl group having 1 to 10 carbon atoms are those represented by the following formula: The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms. Above R 4 is preferably a hydrogen atom, an alkyl group, or an acetyl group, and more preferably a hydrogen atom.

[0049] In the above general formula (2), m is an arbitrary integer of 1 or more. 2 may be the same or different. 3 may be the same or different. That is, the polysilsesquioxane is a polysilsesquioxane having R 2 and R 3 and each of them may be a compound containing two or more different groups.

[0050] Specific examples of the basic skeleton represented by the above general formula (2) include, for example, [R 2 SiO 1.0 (OR 4 )] m (R 2 and R 4 is the same as above.)

[0051] The basic skeleton represented by the above general formula (2) is composed of structural units represented by the following general formula (2'). [R 2 R 3 SiO 1.0 ] (2') (In the formula, R 2 and R 3 is R in the above general formula (2). 2 and R 3 are the same as

[0052] In the polysilsesquioxane, the content of the structural unit represented by the general formula (2') is preferably 1 to 60 mol%, more preferably 5 to 50 mol%, and even more preferably 10 to 30 mol%, based on 100 mol% of all structural units of the polysilsesquioxane. The amount of the structural unit represented by the above general formula (2') is 29 It can be determined by Si-NMR.

[0053] When the polysilsesquioxane further contains a basic skeleton represented by the general formula (2) above, the content of the structural unit represented by the general formula (2') above is preferably 1 mol% or more and 60 mol% or less, more preferably 5 mol% or more and 50 mol% or less, and even more preferably 10 mol% or more and 40 mol% or less, relative to 100 mol% in total of the structural unit represented by the general formula (1') and the structural unit represented by the general formula (2').

[0054] The polysilsesquioxane further comprises, in addition to the basic structure described above, [R 5 R6 R 7 SiO 0.5 ] p (In the formula, R 5 , R 6 and R 7 are the same or different and each represents an alkyl group having 1 to 10 carbon atoms, an aryl group, a vinyl skeleton-containing group, or -OR 8 The above-mentioned alkyl group and aryl group having 1 to 10 carbon atoms may have a substituent. R 8 represents a hydrogen atom, an alkyl group, an aryl group, or an acetyl group. 5 , R 6 and R 7 may be the same or different.

[0055] As the basic skeleton, for example, R 5 , R 6 and R 7 are each an alkyl group having 1 to 10 carbon atoms, an aryl group, or a vinyl skeleton-containing group; 5 , R 6 and R 7 At least one of them is -OR 8 Among them, the above-mentioned form (2) is preferable, and R 5 , R 6 and R 7 Of these, one is -OR 8 and two of them are an alkyl group having 1 to 10 carbon atoms, an aryl group, or a vinyl skeleton-containing group; R 5 , R 6 and R 7 Of these, two are -OR 8 and one of them is an alkyl group having 1 to 10 carbon atoms, an aryl group, or a vinyl skeleton-containing group (2-2). Above R 5 , R 6 and R 7 an alkyl group having 1 to 10 carbon atoms, an aryl group, a vinyl skeleton-containing group, and -OR 8 As the group, R in the above general formula (2) 2 or R 3an alkyl group having 1 to 10 carbon atoms, an aryl group, a vinyl skeleton-containing group, and -OR 4 and the like. p is an arbitrary integer equal to or greater than 1. p R 5 , R 6 and R 7 may be the same or different. The above [R 5 R 6 R 7 SiO 0.5 ] p The basic skeleton represented by [R 5 R 6 R 7 SiO 0.5 ](R 5 , R 6 , and R 7 is the same as above.) It is composed of a structural unit (M-body structure) represented by the formula:

[0056] The polysilsesquioxane may have any of a random structure, a ladder structure, and a cage structure. Among these, it is preferable that the polysilsesquioxane has a ladder structure or a cage structure, since this can further improve resistance to thermal decomposition.

[0057] The polysilsesquioxane preferably has a weight average molecular weight of 1,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 5,000 to 20,000, in that the toughness of the cured product can be improved. The weight average molecular weight can be determined by gel permeation chromatography (GPC) measurement, specifically, by the method described in the examples below.

[0058] The above polysilsesquioxane can be synthesized by subjecting a trialkoxysilane compound to a hydrolysis-condensation reaction. The trialkoxysilane compound may be a compound represented by the following general formula (3).

[0059] R9 Si(OR 10 )3(3) (In the formula, R 9 is the above-mentioned R 1 R represents a group similar to 10 represents an alkyl group, an aryl group, or an acetyl group. 10 may be the same or different.) Above R 10 The alkyl group and aryl group represented by the formula (1) are 1 Preferred examples of the alkyl group and the aryl group are the same as those represented by the following formula:

[0060] In the above general formula (3), three (OR 10 ) may be the same or different, but is preferably the same. 10 ) in R 10 is preferably an alkyl group or an acetyl group, and more preferably an alkyl group.

[0061] Above R 10 The alkyl group represented by the following formula (I) preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and further preferably 1 or 2 carbon atoms.

[0062] Specific examples of the trialkoxysilane compound include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, methyltriisopropoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane, n-decyltrimethoxysilane, n-octyltriethoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane, and n-decyltrimethoxysilane. Examples of the alkyl trialkoxysilane include silane and n-decyl triethoxysilane; aryl trialkoxysilanes such as phenyl trimethoxysilane, phenyl triethoxysilane, parastyryl trimethoxysilane, parastyryl triethoxysilane; and vinyl skeleton-containing trialkoxysilanes such as vinyl triethoxysilane, vinyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-acryloxypropyl triethoxysilane, allyl trimethoxysilane, and allyl triethoxysilane. The above trialkoxysilane compounds may be used alone or in combination of two or more kinds.

[0063] When synthesizing a polysilsesquioxane further containing the basic skeleton represented by the above general formula (2), the polysilsesquioxane can be synthesized by subjecting a mixture containing the above trialkoxysilane compound and dialkoxysilane compound to a hydrolysis-condensation reaction.

[0064] The dialkoxysilane compound may be a compound represented by the following general formula (4). R 11 R 12 Si(OR 13 )2(4) (In the formula, R 11 is the above-mentioned R 2 R represents a group similar to 12 is the above-mentioned R3 R represents a group similar to 11 and R 12 may be the same or different. 13 represents an alkyl group, an aryl group, or an acetyl group. 13 may be the same or different.)

[0065] Above R 13 The alkyl group and aryl group represented by the formula (2) are 4 Preferred examples of the alkyl group and the aryl group are the same as those represented by the following formula:

[0066] In the above general formula (4), two (OR 13 ) may be the same or different, but is preferably the same. 13 ) in R 13 is preferably an alkyl group or an acetyl group, and more preferably an alkyl group.

[0067] Above R 13 The alkyl group represented by the following formula (I) preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and further preferably 1 or 2 carbon atoms.

[0068] Specific examples of the dialkoxysilane compound include dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, methylethyldimethoxysilane, methylpropyldimethoxysilane, methylbutyldimethoxysilane, methylpentyldimethoxysilane, methylhexyldimethoxysilane, methylheptyldimethoxysilane, methyloctyldimethoxysilane, methylnonyldimethoxysilane, methyldecyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, methylethyldiethoxysilane, methylpropyldiethoxysilane, methylbutyldiethoxysilane, methylpentyldiethoxysilane, methylhexyldiethoxysilane, methylheptyldiethoxysilane, methyloctyldiethoxysilane, methylnonyldiethoxysilane, methyldecyldiethoxysilane, methylethyldipropoxysilane, methylpropyldipropoxysilane, alkyl dialkoxysilanes such as methyl butyl dipropoxysilane, methyl pentyl dipropoxysilane, methyl hexyl dipropoxysilane, methyl heptyl dipropoxysilane, methyl octyl dipropoxysilane, methyl nonyl dipropoxysilane, methyl decyl dipropoxysilane, dimethyl dipropoxysilane, diethyl dipropoxysilane, and dipropyl dipropoxysilane; alkyl aryl dialkoxysilanes such as methyl phenyl dimethoxysilane, methyl naphthyl dimethoxysilane, methyl benzyl dimethoxysilane, methyl phenyl diethoxysilane, methyl naphthyl diethoxysilane, methyl benzyl diethoxysilane, methyl phenyl dipropoxysilane, methyl naphthyl dipropoxysilane, and methyl benzyl dipropoxysilane; and diaryl dialkoxysilanes such as diphenyl dimethoxysilane, diphenyl diethoxysilane, and diphenyl dipropoxysilane. Among these, dimethyldiethoxysilane is preferred because it is readily available as an industrial product and is easy to synthesize. The dialkoxysilane compounds may be used alone or in combination of two or more kinds.

[0069] The method for subjecting the trialkoxysilane compound or dialkoxysilane compound to a hydrolysis / condensation reaction is not particularly limited, and any known method can be used, such as a method of heating the trialkoxysilane compound or a mixture of the trialkoxysilane compound and the dialkoxysilane compound in the presence of water to cause the reaction.

[0070] In the above hydrolysis and condensation reaction, the amount of water used is preferably 0.5 to 10.0 mol, more preferably 0.5 to 5.0 mol, and even more preferably 0.5 to 2.0 mol, per mol of alkoxyl group contained in the above trialkoxysilane compound or dialkoxysilane compound as the raw material.

[0071] The heating temperature is preferably from 40 to 200°C, more preferably from 50 to 180°C, and further preferably from 60 to 180°C. The reaction time is preferably from 1 to 40 hours, more preferably from 2 to 30 hours, and further preferably from 4 to 20 hours.

[0072] A preferred heating method is, for example, a method in which a solution obtained by mixing the trialkoxysilane compound or the mixture, water, a solvent, and the like is first heated to 60 to 80° C., and then the temperature is increased to 120 to 180° C., and the solution is maintained for about 4 to 20 hours. This heating method can promote the hydrolysis and condensation reaction, and can produce a polysilsesquioxane containing a larger amount of the basic skeleton represented by the general formula (1) above. The temperature is increased preferably at a rate of 5 to 20° C. / hour, and more preferably at a rate of 5 to 10° C. / hour.

[0073] The hydrolysis and condensation reaction can be carried out in air, but the hydrolysis and condensation reaction of the trialkoxysilane compound and dialkoxysilane compound having an aryl group or an alkyl group is preferably carried out in an inert gas atmosphere such as nitrogen, argon, etc. The hydrolysis and condensation reaction of the trialkoxysilane compound and dialkoxysilane compound having a vinyl group skeleton-containing group is preferably carried out under bubbling of a mixed gas of oxygen / nitrogen=7 / 93 (v / v).

[0074] In the above hydrolysis and condensation reaction, commonly used known components such as a solvent, a catalyst, a surfactant, etc. may be further used.

[0075] Examples of the solvent include the following solvents, and one or more of these may be used. Water; monoalcohols such as methanol, ethanol, isopropanol, n-butanol, and s-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; glycol monoethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and 3-methoxybutanol; glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, and propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, and other glycol monoether esters; alkyl esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate, and ethyl acetoacetate;Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, etc.; aliphatic hydrocarbons such as hexane, cyclohexane, octane, etc.; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.;

[0076] Examples of the catalyst include phosphorus compounds, inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, acetic acid, oxalic acid, citric acid, and propionic acid. Examples of the phosphorus compound include the phosphorus-containing compounds described below. Among them, in terms of facilitating hydrolysis of trialkoxysilane, phosphate compound, phosphinate compound, and phosphonate compound are preferred, phosphate compound and phosphonate compound are more preferred, and phosphate compound is even more preferred.As the phosphate compound, phosphinate compound, and phosphonate compound, the compounds described below can be mentioned.Among them, as the phosphorus compound, triphenylphosphine, phenylphosphonic acid, 2-ethylhexyl phosphate, diphenyl phosphate, etc. can be mentioned as preferred.

[0077] In the synthesis of the polysilsesquioxane, other steps may be carried out after the hydrolysis / condensation reaction step. Examples of the other steps include an aging step, a deactivation step, a dilution step, a concentration step, and a purification step, and these steps may be carried out by known methods.

[0078] The content of the polysilsesquioxane is preferably 50 to 99.95% by mass relative to 100% by mass of the total solid content of the polysilsesquioxane composition. In terms of further improving thermal decomposition resistance and further improving thermal curing, the content of the polysilsesquioxane is more preferably 60% by mass or more, even more preferably 70% by mass or more, more preferably 99.5% by mass or less, even more preferably 99% by mass or less, and even more preferably 98% by mass or less, relative to 100% by mass of the total solid content of the polysilsesquioxane composition.

[0079] The polysilsesquioxane composition of the present invention further contains at least one compound selected from the group consisting of a phosphorus-containing compound, a triazine thiol compound, a hydroxyl group-containing compound having a boiling point of 230° C. or higher, and a carboxy group-containing compound having a boiling point of 230° C. or higher. By including the above compound, the compound functions not only as a condensation catalyst but also as a heat resistance improver, and the thermal decomposition resistance can be improved. In addition, since the thermal decomposition resistance can be improved, the curing at a relatively high temperature becomes good, and the adhesion of the obtained cured product to a metal substrate can be improved.

[0080] <Phosphorus-containing compounds> In the present invention, the phosphorus-containing compound is at least one compound selected from the group consisting of a phosphine compound, a phosphate compound, a phosphinate compound, and a phosphonate compound.

[0081] (Phosphine compounds) The phosphine compound may be a compound represented by the following formula (5).

[0082] [ka] (In the formula, R 14 , R 15 and R 16 are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent.

[0083] The monovalent hydrocarbon group may be either linear or cyclic, but is preferably cyclic in that it results in less decrease in the surface hardness of the cured product. The monovalent hydrocarbon group may be either saturated or unsaturated, but is preferably unsaturated in that there is only a small decrease in the surface hardness of the cured product.

[0084] The monovalent hydrocarbon group includes an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, or a group formed by combining these groups. Examples of the alkyl group include the alkyl groups described above.

[0085] Examples of the alkenyl group include vinyl, n-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 3-methyl-1-butenyl, and 1-hexenyl.

[0086] Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclopropyl, 1-ethylcyclopropyl, 1-propylcyclopropyl, and the like.

[0087] Examples of the cycloalkenyl group include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, cycloheptenyl, and the like.

[0088] Examples of the aryl group include the aryl groups described above.

[0089] Of these, the monovalent hydrocarbon group is preferably a phenyl group.

[0090] The monovalent hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably has 2 to 10 carbon atoms, and further preferably has 4 to 8 carbon atoms.

[0091] The monovalent hydrocarbon group may have a substituent, and examples of the substituent include an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkylamino group, and a hydroxy group. The above-mentioned substituent preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.

[0092] Specific examples of the phosphine compound include triphenylphosphine, tri-orthotolylphosphine, trimethotolylphosphine, tri-paratolylphosphine, tris-paramethoxyphenylphosphine, diphenylcyclohexylphosphine, tricyclohexylphosphine, tri-n-butylphosphine, tri-t-butylphosphine, tri-n-octylphosphine, dicyclohexylphosphine, diphenylisopropylphosphine, trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tridecylphosphine, tridodecylphosphine, etc. Among them, triphenylphosphine, tris-paramethoxyphenylphosphine, diphenylcyclohexylphosphine, tricyclohexylphosphine, and dicyclohexylphosphine are preferred in terms of small decrease in transparency and surface hardness of the cured product, and triphenylphosphine is more preferred in terms of ease of availability.

[0093] The phosphine compound preferably has a boiling point of 100° C. or higher. When the boiling point is 100° C. or higher, the compound is less likely to volatilize when heated, and is therefore highly effective as a heat resistance improver. The phosphine compound more preferably has a boiling point of 150° C. or higher, and even more preferably has a boiling point of 200° C. or higher.

[0094] (Phosphate Compounds) The phosphate compound includes a compound represented by the following formula (6).

[0095] [ka] (In the formula, R 17 , R 18 and R 19 are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent.

[0096] R 17 , R 18 and R 19 The optionally substituted monovalent hydrocarbon group represented by the formula (5) is R 14 ~R 16 Examples of the monovalent hydrocarbon group which may have a substituent include the monovalent hydrocarbon group represented by the following formula: Among them, R 17 , R 18 , and R 19 In terms of minimizing the decrease in transparency of the cured product, the alkyl group is preferably an alkyl group or an aryl group, and in the case of an alkyl group, an alkyl group having 4 to 12 carbon atoms is more preferred, and an alkyl group having 6 to 8 carbon atoms is even more preferred. Furthermore, in the case of an aryl group, a phenyl group is more preferred.

[0097] Specific examples of the phosphate compound include phosphoric acid triesters, phosphoric acid diesters, and phosphoric acid monoesters. Examples of the phosphate triester include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, triisobutyl phosphate, triamyl phosphate, trihexyl phosphate, tris(2-ethylhexyl) phosphate, trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, tricresyl phosphate, triphenyl phosphate, and cresylphenyl phosphate. Examples of the phosphoric acid diester include dimethyl phosphate, diethyl phosphate, dipropyl phosphate, diisopropyl phosphate, dibutyl phosphate, diisobutyl phosphate, diamyl phosphate, dihexyl phosphate, di-2-ethylhexyl phosphate, dioctyl phosphate, didecyl phosphate, didodecyl phosphate, and diphenyl phosphate. Examples of the phosphoric acid monoester include monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, monoisopropyl phosphate, monobutyl phosphate, monoisobutyl phosphate, monoamyl phosphate, monohexyl phosphate, mono-2-ethylhexyl phosphate, monooctyl phosphate, monodecyl phosphate, monododecyl phosphate, and monophenyl phosphate.

[0098] Among these, phosphoric acid diesters and phosphoric acid monoesters are preferred because they can also be used as condensation catalysts in the hydrolysis and condensation reactions of trialkoxysilanes during the preparation of polysilsesquioxanes, and because they make it easier to obtain a composition containing a phosphorus-containing compound during the preparation of polysilsesquioxanes. Among the phosphoric acid diesters, di-2-ethylhexyl phosphate, dioctyl phosphate, and diphenyl phosphate, which have low hydrolyzability, are more preferred. Among the phosphoric acid monoesters, mono-2-ethylhexyl phosphate, monooctyl phosphate, and monophenyl phosphate are more preferred.

[0099] The thermal decomposition temperature of the phosphate compound is preferably 100° C. or higher. When the thermal decomposition temperature is within the above range, the decrease in heat resistance to coloration can be suppressed. The thermal decomposition temperature of the phosphate compound is more preferably 150° C. or higher, and even more preferably 200° C. or higher, in order to suppress the decrease in heat resistance to coloration. The upper limit of the thermal decomposition temperature of the phosphate compound is not particularly limited, but is preferably 400° C. or lower in order to suppress the decrease in heat resistance to coloration. The thermal decomposition temperature can be determined by a method for measuring the thermal weight loss using a thermogravimetric analyzer.

[0100] (Phosphinate compounds) The phosphinate compound includes a compound represented by the following formula (7).

[0101] [ka] (In the formula, R 20 , R 21 and R22 are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent.

[0102] R 20 , R 21 and R 22 The monovalent hydrocarbon group which may have a substituent represented by the formula (5) is R 14 ~R 16 Examples of the monovalent hydrocarbon group which may have a substituent include the monovalent hydrocarbon group represented by the following formula: Among them, R 20 , R 21 and R 22 In terms of minimizing the decrease in transparency of the cured product, the alkyl group is preferably an alkyl group or an aryl group, and in the case of an alkyl group, an alkyl group having 3 to 10 carbon atoms is more preferable, and an alkyl group having 4 to 8 carbon atoms is even more preferable. In addition, in the case of an aryl group, a phenyl group is preferable.

[0103] Specific examples of the phosphinate compound include methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, isobutylphosphinic acid, amylphosphinic acid, hexylphosphinic acid, 2-ethylhexylphosphinic acid, octylphosphinic acid, decylphosphinic acid, dodecylphosphinic acid, phenylphosphinic acid, tolylphosphinic acid, xylylphosphinic acid, biphenylylphosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid, diisopropylphosphinic acid, dibutylphosphinic acid, diisobutylphosphinic acid, diamylphosphinic acid, dihexylphosphinic acid, di-2-ethylhexylphosphinic acid, dioctylphosphinic acid, didecylphosphinic acid, didodecylphosphinic acid, diphenylphosphinic acid, dibiphenylylphosphinic acid, naphthylphosphinic acid, anthrylphosphinic acid, alkyl esters or aryl esters thereof, and metal salts thereof. Among these, in terms of causing only a small decrease in transparency of the cured product and also causing only a small decrease in surface hardness, preferred are hexylphosphinic acid, 2-ethylhexylphosphinic acid, octylphosphinic acid, phenylphosphinic acid, tolylphosphinic acid, and xylylphosphinic acid, more preferred are phenylphosphinic acid, tolylphosphinic acid, and xylylphosphinic acid, and even more preferred is phenylphosphinic acid.

[0104] (Phosphonate Compounds) The phosphonate compound may be a compound represented by the following formula (8).

[0105] [ka] (In the formula, R 23 , R 24 and R 25 are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent.

[0106] R 23 , R 24 and R 25 The monovalent hydrocarbon group which may have a substituent represented by the formula (5) is R 14 ~R 16 Examples of the monovalent hydrocarbon group which may have a substituent include the monovalent hydrocarbon group represented by the following formula: Among them, R 23 , R 24 and R 25 is preferably a hydrogen atom, an alkyl group, or an aryl group, in that the decrease in transparency of the cured product is small, and in the case of an alkyl group, an alkyl group having 4 to 12 carbon atoms is more preferable, and an alkyl group having 6 to 8 carbon atoms is even more preferable. Furthermore, in the case of an aryl group, a phenyl group is more preferable.

[0107] Specific examples of the phosphonate compound include dimethyl phosphonate, diethyl phosphonate, diphenyl phosphonate, dimethylmethyl phosphonate, dipropyl phosphonate, diisopropyl phosphonate, dibutyl phosphonate, isobutyl phosphonate, diamyl phosphonate, dihexyl phosphonate, di-2-ethylhexyl phosphonate, dioctyl phosphonate, didecyl phosphonate, didodecyl phosphonate, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, isobutylphosphonic acid, amylphosphonic acid, hexylphosphonic acid, 2-ethylhexylphosphonic acid, octylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, tolylphosphonic acid, xylylphosphonic acid, biphenylphosphonic acid, naphthylphosphonic acid, anthrylphosphonic acid, and alkyl or aryl esters thereof. In order to minimize the decrease in transparency of the cured product, the alkyl group of the alkyl ester preferably has 1 to 3 carbon atoms, and the aryl ester preferably has a phenyl group. Among these, in terms of minimizing the decrease in transparency of the cured product, hexylphosphonic acid, 2-ethylhexylphosphonic acid, octylphosphonic acid, decylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, and tolylphosphonic acid are preferred, 2-ethylhexylphosphonic acid, octylphosphonic acid, and phenylphosphonic acid are more preferred, and phenylphosphonic acid is even more preferred.

[0108] Among these, the phosphorus-containing compound is preferably a phosphate compound, a phosphinate compound, or a phosphonate compound, more preferably a phosphate compound or a phosphonate compound, and even more preferably a phosphate compound, in that the thermal decomposition resistance of the polysilsesquioxane composition is further improved.

[0109] The polysilsesquioxane composition may contain only one type of the phosphorus-containing compound, or may contain two or more types of the phosphorus-containing compound.

[0110] <Triazine thiol compounds> Examples of the triazine thiol compound include 1,3,5-triazine-2,4,6-trithiol, 2-(dibutylamino)-1,3,5-triazine-4,6-dithiol (also known as "6-(dibutylamino)-1,3,5-triazine-2,4-dithiol"), 6-diallylamino-1,3,5-triazine-2,4-dithiol, 6-(4-vinylbenzyl-n-propyl)amino-1,3,5-triazine-2,4-dithiol, 6-(diisopropylamino)-1,3,5-triazine-2,4-dithiol, 6-(diisobutylamino)-1,3,5-triazine-2,4-dithiol, 6-di(2 6-(ethylhexyl)amino-1,3,5-triazine-2,4-dithiol, 6-(allylamino)-1,3,5-triazine-2,4-dithiol, 6-(diethylamino)-1,3,5-triazine-2,4-dithiol, 6-(butylamino)-1,3,5-triazine-2,4-dithiol, 6-(hexylamino)-1,3,5-triazine-2,4-dithiol, 6-(cyclohexylamino)-1,3,5-triazine-2,4-dithiol, 6-(phenylamino)-1,3,5-triazine-2,4-dithiol, and 6-(anilino)-1,3,5-triazine-2,4-dithiol. Among these, dithiols are preferred because of their high affinity with polysilsesquioxane, and 6-(diisopropylamino)-1,3,5-triazine-2,4-dithiol and 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol are more preferred.

[0111] <Hydroxyl-containing compounds with boiling points of 230°C or higher> Examples of the hydroxyl group-containing compound having a boiling point of 230° C. or higher include alkyl alcohols having carbon numbers of C10 to C18 and a boiling point of 230° C. or higher, alicyclic alcohols having a boiling point of 230° C. or higher, aromatic alcohols having a boiling point of 230° C. or higher, and compounds having a boiling point of 230° C. or higher in which a hydroxyl group is directly bonded to an aromatic ring, etc. The hydroxyl group-containing compound having a boiling point of 230° C. or higher does not include a hindered phenol-based antioxidant, which will be described later. Of the above hydroxyl group-containing compounds, monohydroxy is preferred because of its high affinity with polysilsesquioxane, and 1-naphthol, 2-naphthol, 4-phenylbenzyl alcohol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, and N,N-dimethylaminophenol are more preferred.

[0112] <Carboxy group-containing compounds with boiling points of 230°C or higher> Examples of the carboxyl group-containing compound having a boiling point of 230° C. or higher include C8 to C18 alkyl carboxylic acids having a boiling point of 230° C. or higher, alicyclic carboxylic acids having a boiling point of 230° C. or higher, and aromatic carboxylic acids having a boiling point of 230° C. or higher. As the carboxy group-containing compound, monocarboxylic acids are preferred because of their high affinity with polysilsesquioxane, and cyclohexanecarboxylic acid, benzoic acid, 3-phenylbenzoic acid, 4-phenylbenzoic acid, 1-naphthoic acid, and 2-naphthoic acid are more preferred.

[0113] The polysilsesquioxane composition may contain only one or two or more of the phosphorus-containing compound, triazine thiol compound, hydroxyl group-containing compound having a boiling point of 230° C. or higher, and carboxy group-containing compound having a boiling point of 230° C. or higher.

[0114] The total content of the phosphorus-containing compound, triazine thiol compound, hydroxyl group-containing compound having a boiling point of 230° C. or more, and carboxy group-containing compound having a boiling point of 230° C. or more is preferably 0.05 to 50% by mass relative to 100% by mass of the total solid content of the polysilsesquioxane composition. In terms of improving the heat resistance of the cured product, the content of the compounds is more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and more preferably 20% by mass or less, even more preferably 15% by mass or less, and even more preferably 10% by mass or less. Furthermore, the total content of the phosphorus-containing compound, triazine thiol compound, hydroxyl group-containing compound, and carboxy group-containing compound is more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1 to 10 mass%, relative to 100 mass% of the total solid content of the polysilsesquioxane composition.

[0115] <Hindered phenol-based antioxidant> The polysilsesquioxane composition of the present invention preferably further contains a hindered phenol-based antioxidant. By containing a hindered phenol-based antioxidant, crack resistance due to heat (thermal crack resistance) can be improved. The hindered phenol antioxidant is a phenolic compound having at least one phenolic hydroxyl group and having a sterically hindered substituent on one or both of the two carbon atoms adjacent to the carbon atom having the phenolic hydroxyl group. The sterically hindered substituent refers to a bulky substituent such as a branched or cyclic alkyl group having 4 or more carbon atoms, such as a t-butyl group.

[0116] Examples of the hindered phenol-based antioxidant include 1,3,5-tris[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by ADEKA Corporation, trade name: Adeka STAB AO-20), 1,1,3-tris(2-methyl-4-hydroxy-5-tertiary butylphenyl)butane (manufactured by ADEKA Corporation, trade name: Adeka STAB AO-30), 4,4'-butylidenebis(6-tertiary butyl-m-cresol) (manufactured by ADEKA Corporation, trade name: Adeka STAB AO-40), and 3-(3,5-di-tertiary butyl-4-hydroxyphenyl)stearyl propionate (manufactured by ADEKA Corporation, trade name: Adeka STAB AO-40). Examples of such esters include 2,2'-dimethyl-2,2'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dipropane-1,1'-diyl bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (manufactured by ADEKA Corporation, trade name: Adeka STAB AO-50), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by ADEKA Corporation, trade name: Adeka STAB AO-60), 2,2'-dimethyl-2,2'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dipropane-1,1'-diyl bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propinoate] (manufactured by ADEKA Corporation, trade name: Adeka STAB AO-80), and 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene (manufactured by ADEKA Corporation, trade name: Adeka STAB AO-330).

[0117] Among them, 1,3,5-tris[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by ADEKA Corporation, trade name: Adeka STAB AO-20), 2,2'-dimethyl-2,2'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dipropane-1,1' -diyl=bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (ADEKA Corporation, trade name: Adeka STAB AO-80), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADEKA Corporation, trade name: Adeka STAB AO-60), 2,4,6-tris(3',5'-di Preferred are hindered phenol-based antioxidants having a 1% weight loss temperature of 300° C. or higher under a nitrogen atmosphere, such as 1,3,5-tris[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (ADEKA Corporation, trade name: Adeka STAB AO-20) and 2,2′-dimethyl-2,2′-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dipropane-1,1′-diyl bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propinoate] (ADEKA Corporation, trade name: Adeka STAB AO-80) are more preferred.

[0118] The content of the hindered phenol-based antioxidant is preferably 0.01 to 10 mass%, more preferably 0.1 to 5 mass%, and even more preferably 0.3 to 2 mass%, relative to 100 mass% of the total solid content of the polysilsesquioxane composition.

[0119] <Other ingredients> The polysilsesquioxane composition of the present invention may further contain other components in addition to the above-mentioned components, as long as the effects of the present invention are not affected. Examples of the other components include solvents, coloring materials (pigments, dyes), dispersants, heat resistance improvers, leveling agents, inorganic fine particles such as silica, titanium, and zirconia fine particles, organic fine particles such as acrylic, polystyrene, and polyolefin fine particles, coupling agents such as silane-based, aluminum-based, and titanium-based, fillers, resins, plasticizers, polymerization initiators, heat curing agents, polymerization inhibitors, ultraviolet absorbers, antioxidants other than hindered phenol-based antioxidants, matting agents, antifoaming agents, antistatic agents, slip agents, surface modifiers, thixotropic agents, polymerizable compounds, and acid generators. These may be used alone or in combination of two or more. These components may be appropriately selected from known ones and used, and the amount used may be appropriately set.

[0120] <Preparation of Polysilsesquioxane Composition> The polysilsesquioxane composition of the present invention can be prepared by mixing the above-mentioned polysilsesquioxane with at least one compound selected from the group consisting of the above-mentioned phosphorus-containing compound, triazine thiol compound, hydroxyl group-containing compound having a boiling point of 230° C. or higher, and carboxy group-containing compound having a boiling point of 230° C. or higher, and other components as necessary. The mixing method is not particularly limited, and examples thereof include a method in which the above-mentioned components are mixed and dispersed using a known mixer or disperser.

[0121] <Cured product> The method for obtaining a cured product using the polysilsesquioxane composition of the present invention is not particularly limited, and any known method may be used. For example, a method may be used in which the polysilsesquioxane composition is applied to a substrate, and the applied composition is heated or irradiated with active energy rays such as ultraviolet rays, or a combination of these is used to cure the composition to obtain a cured product.

[0122] The material of the base material (substrate) is not particularly limited and may be appropriately selected depending on the purpose and use, and may be, for example, an inorganic material, an organic material, a mixture thereof, or an organic-inorganic composite material. Among these, inorganic materials are preferred.

[0123] The inorganic material may be metal, glass, or the like, with metal-containing compounds being preferred. The metal-containing compound may be a metal or a compound containing a metal, such as a metal, a metal oxide, a metal nitride, or a metal carbide.

[0124] Preferred examples of the metal include silicon wafer, copper, aluminum, and SUS. Preferred examples of the metal oxide include silica, titania, ITO (tin-doped indium oxide), and indium zinc oxide (IZO). A preferred example of the metal nitride is silicon nitride. As the organic material, a conventionally known resin can be used. The substrate is preferably in the form of a plate, and a plate-shaped substrate made of the above-mentioned preferred materials is particularly preferred.

[0125] The method for applying the polysilsesquioxane composition to form a coating film is not particularly limited, and can be any known method such as spin coating, gravure coating, dip coating, slot die coating, or spray coating.

[0126] The heating temperature is not particularly limited and may be appropriately selected depending on the composition of the polysilsesquioxane composition, but is usually 50 to 500°C, preferably 80 to 450°C, and more preferably 100 to 400°C.

[0127] Irradiation with active energy rays is not particularly limited as long as it is a method capable of irradiating radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays, and can be carried out by a known method. For example, it can be carried out using lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers.

[0128] When the cured product is a cured film, the film thickness is preferably from 1 to 1000 μm, more preferably from 5 to 200 μm, and even more preferably from 10 to 100 μm.

[0129] The cured product thus obtained has excellent resistance to thermal decomposition and excellent adhesion to metal substrates. The metal substrate may be a substrate made of the above-mentioned metal-containing compound. In particular, the metal substrate is preferably a substrate made of a metal and / or a metal oxide, and more preferably a substrate made of a metal. A cured product obtained by curing the above-mentioned polysilsesquioxane composition also constitutes one aspect of the present invention.

[0130] <Application> The polysilsesquioxane composition of the present invention can provide a cured product having excellent thermal decomposition resistance and adhesion to a metal substrate. Furthermore, by using a specific polysilsesquioxane, a cured product having excellent transparency and flexibility can be provided. Therefore, the polysilsesquioxane composition of the present invention can be suitably used in applications requiring thermal decomposition resistance and adhesion to a metal substrate, and applications requiring further transparency and flexibility. Examples of such applications include optical materials (members), machine part materials, electric and electronic part materials, automobile part materials, civil engineering and construction materials, molding materials, and various applications such as paints and adhesive materials. The polysilsesquioxane composition of the present invention is preferably used for optical materials or low dielectric materials.

[0131] Specific examples of the uses of the polysilsesquioxane composition of the present invention include, for example, imaging lenses for cameras, encapsulants for LEDs, optical adhesives, joining materials for optical transmission, filters, diffraction gratings, prisms, optical waveguides, watch glasses, cover glasses for display devices, etc., such as transparent glasses and cover glasses for optical applications; optodevice applications such as photosensors, photoswitches, LEDs, light-emitting elements, optical waveguides, multiplexers, demultiplexers, circuit breakers, optical splitters, optical fiber adhesives, etc.; display device applications such as substrates for display elements such as LCDs, organic ELs, and PDPs, substrates for color filters, substrates for touch panels, display protective films, display backlights, light guide plates, antireflection films, antifogging films, etc., and insulating films.

Examples

[0132] Examples are given below to explain the present invention in more detail, but the present invention is not limited only to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0133] In the following synthesis examples, etc., various physical properties, etc. were evaluated as follows. <Weight-average molecular weight> Using polystyrene as a standard substance and tetrahydrofuran as an eluent, the weight-average molecular weight was measured by GPC (gel permeation chromatography) method using HLC-8320GPC (manufactured by Tosoh Corporation), column: TSKgel SuperHZ-N (manufactured by Tosoh Corporation).

[0134] <Solid content> About 1 g of the resin solution was weighed into an aluminum cup, about 3 g of acetone was added and dissolved, and then it was naturally dried at room temperature. Then, using a vacuum dryer (manufactured by Tokyo Rika Kikai Co., Ltd., product name: VOS-301SD type), it was dried at 200 °C for 1 hour under vacuum, cooled in a desiccator, and the mass was measured. From the mass reduction amount, the solid content (% by mass) of the polymer solution was calculated.

[0135] <T structure [R 1 SiO1.5 ] and [CH3CH3SiO 1.0 ]> Approximately 0.3 g of the resin solution was weighed out into a screw tube, and approximately 0.8 g of deuterated dimethyl sulfoxide was added to dissolve it, then the solution was placed in an NMR tube. 29 The measurements were performed using Si-NMR (JNM-ECZ600, manufactured by JEOL Ltd.). 1 SiO 1.5 The amount (mol%) of T-isomer [R 1 SiO 1.5 ], D-body structure [R 2 R 3 SiO 1.0 ]([R 2 SiO 1.0 (OR 4 )], etc.), M-body structure [R 5 R 6 R 7 SiO 0.5 ]([R 5 SiO 0.5 (OR 8 )2], etc.), the area of ​​each peak of the monomer was determined, and the ratio of the area of ​​the T-isomer structure to the total area was calculated. That is, in the case of polysilsesquioxane obtained by hydrolysis and condensation reaction of phenyltrimethoxysilane and methyltriethoxysilane, the homopolymer obtained by hydrolysis and condensation reaction of phenyltrimethoxysilane, the homopolymer obtained by hydrolysis and condensation reaction of methyltriethoxysilane, the phenyltrimethoxysilane, and the methyltriethoxysilane samples were 29 The measurements were performed using Si-NMR. The peaks of the T-form of phenyltrimethoxysilane were observed at -76 to -81 ppm, the D-form at -67 to -72 ppm, the M-form at -60 to -63 ppm, and the monomer at -55 ppm. The peaks of the T-form of methyltriethoxysilane were observed at -63 to -68 ppm, the D-form at -50 to -58 ppm, the M-form at -47 ppm, and the monomer at -38 ppm. The area of ​​each peak was calculated, and the amount of the T-form structure (mol%) was calculated from the ratio of the area of ​​the T-form structure to the total area. The peaks of the T-structure, D-structure, M-structure and monomer of other polysilsesquioxanes were similarly identified, and the area of ​​each peak was determined to determine the amount of the T-structure.

[0136] In Examples 20 to 23, [CH3CH3SiO 1.0 The amount of was also determined in the same manner. That is, in the case of polysilsesquioxane obtained by hydrolysis and condensation reaction of phenyltrimethoxysilane, methyltriethoxysilane, and dimethyldiethoxysilane in Example 20, the peaks of the T-structure, D-structure, M-structure, and monomer of polysilsesquioxane of phenyltrimethoxysilane and methyltriethoxysilane were observed as described above. For dimethyldiethoxysilane, the homopolymer obtained by hydrolysis and condensation reaction of dimethyltriethoxysilane and the respective samples of dimethyldiethoxysilane were observed. 29 Measured by Si-NMR. [CH3CH3SiO 1.0 The D-form structure had peaks at -19 to -22 ppm, the M-form structure had peaks at -16 to -19 ppm, and the monomer had peaks at -3 to -4 ppm. The area of ​​each peak was calculated, and the ratio of [CH3CH3SiO 1.0 From the area ratio of [CH3CH3SiO 1.0 The amount (mol%) of ] was calculated.

[0137] <Thermal decomposition resistance (thermal weight loss (%))> Approximately 30 mg of the resin solution was weighed out into an aluminum pan, and using a TGA-50 / 50H (manufactured by Shimadzu Corporation), the temperature was raised from room temperature to 200°C at 20°C / min. Then, the temperature was held at 200°C for 1 hour, and then the temperature was raised from 200°C to 400°C at 10°C / min. The thermal weight loss (%) after holding at 400°C for 3 hours was calculated by determining the weight loss from after holding at 200°C for 1 hour to after holding at 400°C for 3 hours, and the ratio (%) of this weight loss to the resin weight after holding at 200°C for 1 hour was calculated.

[0138] <Adhesion> The resin solution was spin-coated on a copper plate (0.5×50×100 mm, manufactured by Nippon Testpanel Co., Ltd.), dried at 100°C for 30 minutes, and then dried at 200°C for 1 hour to obtain a coating film with a thickness of 20 μm. The obtained coating film was then heat-treated at 200°C for 500 hours. After heating at 200°C for 500 hours, the coating film was evaluated as "◯" if it was not peeled off from the copper plate, after heating at 200°C for 500 hours, the coating film was evaluated as "△" if it was peeled off from the copper plate after heating at 200°C for 500 hours, but was not peeled off from the copper plate after heating at 200°C for 300 hours, and after heating at 200°C for 300 hours, the coating film was evaluated as "×".

[0139] <Transparency> The resin solution was spin-coated onto a 5 cm square glass substrate, dried at 100°C for 30 minutes, and then dried at 200°C for 1 hour to obtain a coating film with a thickness of 25 μm. The coating film was visually evaluated, and coating films without haze (cloudiness) and clear (transparent) were rated as "good", and those with haze were rated as "poor".

[0140] <Bending test> The resin solution was spin-coated on a copper plate, dried at 100°C for 30 minutes, and then dried at 200°C for 1 hour to obtain a coating film with a thickness of 20 μm. Then, the opposite side of the coating film on the copper plate was bent using a coating film bending tester No. 514 (manufactured by Yasuda Seiki Seisakusho, Φ4 mm) until the angle formed by the copper plate was about 90 degrees, and the state of the coating film was observed. When the angle was about 90 degrees, the coating film was not peeled or cracked, and when the angle was about 90 degrees, the coating film was peeled or cracked, but when the angle was about 45 degrees, the coating film was not peeled or cracked, and when the angle was about 45 degrees, the coating film was ...

[0141] <Heat crack resistance> The polysilsesquioxane composition was applied to a silicon wafer, dried at 100°C for 30 minutes, and then dried at 250°C for 1 hour to obtain a coating film having a thickness of 20 μm. The obtained coating film was subjected to a heat treatment at 400°C in a nitrogen atmosphere. Coatings in which cracks were observed after 1 hour of heat treatment were evaluated as "x", coatings in which cracks were observed after 2 hours of heat treatment were evaluated as "△", and coatings in which cracks were not observed even after 2 hours of heat treatment were evaluated as "◯".

[0142] (Synthesis Example 1) In a reaction vessel, 55.7 parts of diethylene glycol ethyl methyl ether, 100 parts of phenyltrimethoxysilane, and 29.97 parts of methyltriethoxysilane were charged, and 54.53 parts of water was added while stirring and purging with nitrogen, and the temperature was raised to 80 ° C. Then, the temperature was raised from 80 ° C. to 160 ° C. at a rate of 10 ° C. / hour while distilling off diethylene glycol ethyl methyl ether and water, and after reaching 160 ° C., the reaction was carried out at 160 ° C. for 12 hours to obtain a resin solution (polysilsesquioxane solution) 1. The physical properties of the obtained resin solution are shown in Table 1.

[0143] (Synthesis Examples 2 to 4) As shown in Table 1, the type of trialkoxysilane compound used was changed, and the charged composition was changed, but the reaction was carried out in the same manner as in Synthesis Example 1, to obtain resin solutions 2 to 4.

[0144] (Synthesis Example 5) A reaction vessel was charged with 55.7 parts of diethylene glycol ethyl methyl ether, 100 parts of phenyltrimethoxysilane, and 29.97 parts of methyltriethoxysilane, and the mixture was replaced with nitrogen and stirred while adding 54.53 parts of water and 0.26 parts of 2-ethylhexyl phosphate (mono- and diester mixture, manufactured by Tokyo Chemical Industry Co., Ltd.), and the temperature was raised to 80° C. Thereafter, the temperature was raised from 80° C. to 160° C. at a rate of 10° C. / hour while distilling off diethylene glycol ethyl methyl ether and water. After reaching 160° C., the reaction was carried out at 160° C. for 12 hours, and resin solution 5 was obtained.

[0145] (Synthesis Examples 6-15, 17-23) As shown in Table 1, the reaction was carried out in the same manner as in Synthesis Example 5 except that the type or amount of the trialkoxysilane compound or phosphorus compound in Synthesis Example 5 was changed, to obtain resin solutions 6 to 15 and 17 to 23.

[0146] (Synthesis Example 16) In a reaction vessel, 46.47 parts of diethylene glycol ethyl methyl ether, 110 parts of phenyl trimethoxysilane, 66.28 parts of n-propyl trimethoxysilane, and 9.6 parts of vinyl triethoxysilane were charged, and while bubbling and stirring an oxygen / nitrogen = 7 / 93 (v / v) mixed gas, 0.06 parts of topanol (6-tert-butyl-2,4-xylenol), 54.53 parts of water, and 0.37 parts of 2-ethylhexyl phosphate (mono- and diester mixture) were added, and the temperature was raised to 80 ° C. Then, the temperature was raised from 80 ° C. to 140 ° C. at 10 ° C. / hour while distilling off diethylene glycol ethyl methyl ether and water, and after reaching 140 ° C., the reaction was carried out at 140 ° C. for 10 hours, and a resin solution 16 was obtained.

[0147] Example 1 0.6 parts of triphenylphosphine was added as an additive to 100 parts (as is) of resin solution 1 to prepare a polysilsesquioxane composition. The obtained polysilsesquioxane composition was evaluated for thermal decomposition resistance, adhesion, transparency, and bending test. The evaluation results are shown in Table 2.

[0148] (Examples 2 to 49 and Comparative Examples 1 to 7) The resin solutions and additives were mixed as shown in Tables 2 to 4, and the same evaluations as in Example 1 were carried out. Examples 27 to 49 and Comparative Examples 5 to 7 were further evaluated for heat cracking. The evaluation results are shown in Tables 2 to 4. The transparency and bending tests for Comparative Example 4 were not possible because the coating film peeled off from the substrate before the evaluation.

[0149] The boiling points of the phosphine compounds shown in Tables 2 and 3 are as follows. Triphenylphosphine (boiling point 360℃) Trioctylphosphine (boiling point 240℃)

[0150] [Table 1]

[0151] [Table 2]

[0152] [Table 3]

[0153] [Table 4]

[0154] From Tables 1 to 4, it was confirmed that the compositions containing the polysilsesquioxanes of the examples and the specified compounds can give cured products excellent in both thermal decomposition resistance and adhesion to metal substrates. The cured products were also confirmed to have excellent transparency. In addition, it was confirmed that the compositions containing polysilsesquioxanes containing an alkyl group having 3 to 10 carbon atoms are also excellent in flexibility. It was also confirmed that the inclusion of a hindered phenol-based antioxidant improves thermal cracking resistance.

[0155] In addition, the polysilsesquioxane composition of Example 1, 9, 11, or 12 was applied to a silicon wafer and a silicon wafer with 300 nm of silicon dioxide attached thereto as substrates, respectively, and dried at 100°C for 30 minutes, and then dried at 200°C for 1 hour to obtain a coating film with a thickness of 20 μm on the surface of each substrate. The obtained coating film was then heat-treated at 400°C for 1 hour in a nitrogen atmosphere, and then a tape peel test of the coating film was performed using cellophane tape. As a result, in all cases, each coating film did not peel off and had good adhesion. A coating film was formed in the same manner and a tape peeling test was performed for the polysilsesquioxane compositions of Comparative Examples 1, 2, and 3. As a result, in all cases, each coating film peeled off both from the silicon wafer and from the silicon wafer with 300 nm of silicon dioxide attached thereto, indicating poor adhesion.

Claims

1. Polysilsesquioxane, The composition comprises at least one compound selected from the group consisting of a phosphorus-containing compound, a triazine thiol compound, a compound having a boiling point of 230° C. or higher and a hydroxyl group directly bonded to an aromatic ring, and a carboxy group-containing compound having a boiling point of 230° C. or higher; the phosphorus-containing compound is at least one selected from the group consisting of a phosphine compound, a phosphate compound, a phosphinate compound, and a phosphonate compound; The polysilsesquioxane is represented by the following general formula (1): [R １ SiO １．５ ] ｎ (1) (In the formula, R １ represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or a vinyl skeleton-containing group. n is an arbitrary number of 1 or more. １ may be the same or different.) R of the general formula (1) １ has at least a skeleton that is an alkyl group having 3 to 10 carbon atoms and a skeleton that is an aryl group A polysilsesquioxane composition comprising:

2. The polysilsesquioxane is represented by the general formula (1) R １ The polysilsesquioxane composition according to claim 1, characterized in that it has at least a skeleton that is a methyl group, a skeleton that is an alkyl group having 3 to 10 carbon atoms, and a skeleton that is an aryl group.

3. The polysilsesquioxane is represented by the general formula (1) R １ The polysilsesquioxane composition according to claim 1, characterized in that it has at least a skeleton that is an alkyl group having 3 to 10 carbon atoms, a skeleton that is an aryl group, and a skeleton that is a vinyl skeleton-containing group.

4. The polysilsesquioxane composition according to any one of claims 1 to 3, characterized in that the carbon amount of the alkyl group having 3 to 10 carbon atoms is 3 mass% or more of the total carbon amount of the polysilsesquioxane.

5. The polysilsesquioxane composition according to any one of claims 1 to 4, characterized in that the polysilsesquioxane contains a structural unit represented by the following general formula (1') in an amount of 40 mol % or more, based on 100 mol % of all structural units of the polysilsesquioxane: [R １ SiO １．５ ] (1’) (In the formula, R １ represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or a vinyl skeleton-containing group.

6. The polysilsesquioxane composition according to any one of claims 1 to 5, characterized in that the polysilsesquioxane further contains a basic skeleton represented by the following general formula (2): [R ２ R ３ SiO １．０ ] ｍ (2) (In the formula, R ２ and R ３ are the same or different and each represents an alkyl group having 1 to 10 carbon atoms, an aryl group, a vinyl skeleton-containing group, or -OR ４ The alkyl group having 1 to 10 carbon atoms and the aryl group may have a substituent. ４ represents a hydrogen atom, an alkyl group, an aryl group, or an acetyl group. ２ and R ３ may be the same or different.)

7. The polysilsesquioxane composition according to any one of claims 1 to 6, wherein the phosphine compound has a boiling point of 100°C or higher.

8. The polysilsesquioxane composition according to any one of claims 1 to 7, further comprising a hindered phenol-based antioxidant.

9. The polysilsesquioxane composition according to any one of claims 1 to 8, which is used for an optical material.

10. The polysilsesquioxane composition according to any one of claims 1 to 8, which is used for a low dielectric material.

11. A cured product obtained by curing the polysilsesquioxane composition according to any one of claims 1 to 10.

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