Polysilsesquioxane compounds, curable compositions, cured products, adhesives, and methods for producing polysilsesquioxane compounds

Abstract

The present invention provides a novel polysilsesquioxane compound that can be used as a curable composition and is also useful in reducing carbon dioxide emissions, a curable composition containing the polysilsesquioxane compound, a cured product obtained by curing the curable composition, an adhesive containing the curable composition, and a method for producing the polysilsesquioxane compound. [Solution] A polysilsesquioxane compound characterized by containing a structural unit having a cyclic carbonate group represented by the following formula (6) within the molecule. TIFF2026061902000021.tif69140

Description

Technical Field

[0001] The present invention relates to a novel polysilsesquioxane compound, a curable composition, a cured product, an adhesive, and a method for producing the above polysilsesquioxane compound.

Background Art

[0002] In recent years, curable compositions have been used as compositions for fixing optical elements such as adhesives for optical elements and encapsulants for optical elements.

[0003] Optical elements include various lasers such as semiconductor lasers (LDs), light-emitting elements such as light-emitting diodes (LEDs), light-receiving elements, compound optical elements, optical integrated circuits, and the like. In recent years, optical elements that emit blue light or white light with a shorter peak wavelength of light emission have been developed and widely used. The brightness of such light-emitting elements with a short peak wavelength of light emission has advanced dramatically, and accordingly, the amount of heat generated by the optical elements tends to further increase.

[0004] However, with the increasing brightness of optical elements in recent years, there has been a problem that the cured product of the composition for fixing optical elements is exposed to light with higher energy or heat at a higher temperature generated from the optical element for a long time, deteriorates, and peels off.

[0005] To solve this problem, in Patent Documents 1 to 3, compositions for fixing optical elements containing a polysilsesquioxane compound as a main component have been proposed.

[0006] The polysilsesquioxane compound is an intermediate substance between inorganic silica [SiO2] and organic silicone [(R2SiO) 3 / 2 , n , n , and is a compound represented by the formula: (RSiO 3 / 2 ) n (wherein R represents an alkyl group, an aryl group, etc., which may have a substituent).

Prior Art Documents

Patent Documents

[0007] [Patent Document 1] Japanese Patent Publication No. 2004-359933 [Patent Document 2] Japanese Patent Publication No. 2005-263869 [Patent Document 3] Japanese Patent Publication No. 2006-328231 [Overview of the project] [Problems that the invention aims to solve]

[0008] Incidentally, in recent years, with the growing demand for the creation of a circular economy, gases such as carbon dioxide, methane, and carbon monoxide have attracted attention as sustainable carbon raw materials. For example, it has been reported that aliphatic polycarbonates, which have only aliphatic (non-aromatic) groups in their main chain, can be produced by copolymerizing carbon dioxide with epoxides, and there is growing interest in chemicals that utilize gases such as carbon dioxide as raw materials, as well as their manufacturing technologies. Since carbon dioxide is considered a cause of global warming, the effective utilization of carbon dioxide emitted from factories during the production of various materials is beneficial for environmental protection.

[0009] The present invention has been made in view of the above circumstances, and aims to provide a novel polysilsesquioxane compound that can be used as a curable composition and is also useful in reducing carbon dioxide emissions, a curable composition containing the polysilsesquioxane compound, a cured product obtained by curing the curable composition, an adhesive containing the curable composition, and a method for producing the polysilsesquioxane compound. [Means for solving the problem]

[0010] To achieve the above objective, firstly, the present invention relates to the following formula (1) [ka] (In the formula, R 1 R represents an alkylene group with 1 to 20 carbon atoms. 2 (This represents an alkylene group with 1 to 10 carbon atoms.) To provide a polysilsesquioxane compound characterized by containing a structural unit represented by (Invention 1).

[0011] In the above invention (Invention 1), the weight average molecular weight is preferably 700 or more and 20,000 or less (Invention 2).

[0012] In the above invention (Inventions 1 and 2), the R 2 is preferably a methylene group (Invention 3).

[0013] Second, the present invention provides a curable composition characterized by containing the polysilsesquioxane compound (Inventions 1 to 3) (Invention 4).

[0014] Third, the present invention provides a cured product characterized by being obtained by curing the curable composition (Invention 4) (Invention 5).

[0015] Fourth, the present invention provides an adhesive containing the curable composition (Invention 4) (Invention 6).

[0016] Fifth, the present invention is a method for producing the polysilsesquioxane compound (Inventions 1 to 3), which is represented by the following formula (2)[[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​3 (This represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms.) The present invention provides a manufacturing method comprising the steps of (I) obtaining a compound having the structure shown by formula (3) and (II) obtaining a polysilsesquioxane compound containing the structural unit shown by formula (1) by polycondensing the compound having the structure shown by formula (3). [Effects of the Invention]

[0017] The polysilsesquioxane compound according to the present invention can be used as a curable composition and is also useful for reducing carbon dioxide emissions. [Brief explanation of the drawing]

[0018] [Figure 1] This figure shows the 1H NMR measurement results of the alkoxysilane prepared in Example 1. [Figure 2] This figure shows the 1H NMR measurement results of the alkoxysilane prepared in Example 1. [Figure 3] This figure shows the 1H NMR measurement results of the alkoxysilane prepared in Example 1. [Figure 4] This figure shows the 13C NMR measurement results of the alkoxysilane prepared in Example 1. [Figure 5] This figure shows the IR measurement results of the alkoxysilane prepared in Example 1. [Figure 6] This figure shows the 1H NMR measurement results of the polysilsesquioxane prepared in Example 1. [Figure 7] This figure shows the 29Si NMR measurement results of the polysilsesquioxane prepared in Example 1. [Figure 8] This figure shows the IR measurement results of the polysilsesquioxane prepared in Example 1. [Figure 9] This figure shows the 1H NMR measurement results of the alkoxysilane prepared in Example 2. [Figure 10] This figure shows the 1H NMR measurement results of the alkoxysilane prepared in Example 2. [Figure 11] This figure shows the 1H NMR measurement results of the alkoxysilane prepared in Example 2. [Figure 12] This figure shows the 1H NMR measurement results of the alkoxysilane prepared in Example 2. [Figure 13] This figure shows the 13C NMR measurement results of the alkoxysilane prepared in Example 2. [Figure 14] This figure shows the IR measurement results of the alkoxysilane prepared in Example 2. [Figure 15] This figure shows the IR measurement results of the polysilsesquioxane prepared in Example 2. [Figure 16] This figure shows the 1H NMR measurement results of the polysilsesquioxane prepared in Example 4. [Figure 17] This figure shows the 29Si NMR measurement results of the polysilsesquioxane prepared in Example 4. [Figure 18] This figure shows the IR measurement results of the polysilsesquioxane prepared in Example 4. [Figure 19] This figure shows the 1H NMR measurement results of the polysilsesquioxane prepared in Example 5. [Figure 20] This figure shows the 29Si NMR measurement results of the polysilsesquioxane prepared in Example 5. [Figure 21] This figure shows the IR measurement results of the polysilsesquioxane prepared in Example 5. [Figure 22] This figure shows the 1H NMR measurement results of the polysilsesquioxane prepared in Example 6. [Figure 23] This figure shows the 29Si NMR measurement results of the polysilsesquioxane prepared in Example 6. [Figure 24] This figure shows the IR measurement results of the polysilsesquioxane prepared in Example 6. [Modes for carrying out the invention]

[0019] Embodiments of the present invention will be described below. [Polysilsesquioxane compounds] The polysilsesquioxane compound according to this embodiment is given by the following formula (1) [ka] (In the formula, R 1 R represents an alkylene group with 1 to 20 carbon atoms. 2 (This represents an alkylene group with 1 to 10 carbon atoms.) It includes the structural units shown.

[0020] As is clear from formula (1) above, the polysilsesquioxane compound according to this embodiment contains the following formula (6) within its molecule. [ka] It has cyclic carbonate groups represented by . Therefore, it can interact with these cyclic carbonate groups within or between molecules, and can undergo reactions mediated by these cyclic carbonate groups. As a result, the polysilsesquioxane compound according to this embodiment is curable both on its own and in the form of a composition containing the compound.

[0021] Furthermore, as will be described later, carbon dioxide can be used as one of the materials when producing the polysilsesquioxane compound according to this embodiment. Therefore, the use of the polysilsesquioxane compound according to this embodiment is useful in reducing carbon dioxide emissions from the viewpoint of carbon neutrality.

[0022] In the structure shown in formula (1) above, R 1 As described above, this is an alkylene group having 1 to 20 carbon atoms, but the number of carbon atoms is particularly preferably 1 to 10, and even more preferably 2 to 9.

[0023] Furthermore, in the structure shown in formula (1) above, R 2As mentioned above, this is an alkylene group having 1 to 10 carbon atoms, but the number of carbon atoms is particularly preferably 1 to 5, and more preferably 1 to 3. In particular, R 2 It is preferable that it is a methylene group.

[0024] The polysilsesquioxane compound according to this embodiment may consist only of the structural unit represented by formula (1) above, or it may consist of the structural unit represented by formula (1) above plus other structural units. In this case, the other structural unit is represented by the following formula (12) [ka] The structural unit may be represented by . In formula (12), R is at least one selected from the group consisting of unsubstituted C1-C10 alkyl groups, substituted C1-C10 alkyl groups, unsubstituted C6-C12 aryl groups, and substituted C6-C12 aryl groups.

[0025] The number of carbon atoms in the "unsubstituted C1-C10 alkyl group" represented by R is preferably 1-6, and more preferably 1-3. Examples of the "unsubstituted C1-C10 alkyl group" include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, and n-decyl group.

[0026] The number of carbon atoms in the "substituted alkyl group having 1 to 10 carbon atoms" represented by R is preferably 1 to 6, and more preferably 1 to 3. Note that this number of carbon atoms refers to the number of carbon atoms in the alkyl group portion excluding the substituent. Therefore, when R is a "substituted alkyl group having 1 to 10 carbon atoms," the number of carbon atoms in R may exceed 10.

[0027] Examples of alkyl groups in "substituted C1-C10 alkyl groups" are the same as those shown as "unsubstituted C1-C10 alkyl groups." The number of substituent atoms (excluding hydrogen atoms) in "substituted C1-C10 alkyl groups" is usually 1-30, preferably 1-20.

[0028] Examples of substituents in "alkyl groups having 1 to 10 carbon atoms with substituents" include halogen atoms such as fluorine, chlorine, and bromine; cyano groups; and groups represented by the formula OG. Here, G represents a protecting group for the hydroxyl group. There are no particular restrictions on the protecting group for the hydroxyl group, and any known protecting group that is known to protect the hydroxyl group can be used. Examples include acyl protecting groups; silyl protecting groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, and t-butyldiphenylsilyl group; acetal protecting groups such as methoxymethyl group, methoxyethoxymethyl group, 1-ethoxyethyl group, tetrahydropyran-2-yl group, and tetrahydrofuran-2-yl group; alkoxycarbonyl protecting groups such as t-butoxycarbonyl group; and ether protecting groups such as methyl group, ethyl group, t-butyl group, octyl group, allyl group, triphenylmethyl group, benzyl group, p-methoxybenzyl group, fluorenyl group, trityl group, and benzhydryl group.

[0029] The "unsubstituted aryl group having 6 to 12 carbon atoms" represented by R preferably has 6 carbon atoms. Examples of "unsubstituted aryl groups having 6 to 12 carbon atoms" include the phenyl group, 1-naphthyl group, and 2-naphthyl group.

[0030] The number of carbon atoms in the "substituted aryl group having 6 to 12 carbon atoms" represented by R is preferably 6. Note that this number of carbon atoms refers to the number of carbon atoms in the aryl group portion excluding the substituent. Therefore, when R is a "substituted aryl group having 6 to 12 carbon atoms," the number of carbon atoms in R may exceed 12.

[0031] Examples of aryl groups in "substituted C6-C12 aryl groups" include those similar to those listed as "unsubstituted C6-C12 aryl groups." Examples of substituents in "substituted C6-C12 aryl groups" include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and isooctyl groups; halogen atoms such as fluorine, chlorine, and bromine atoms; and alkoxy groups such as methoxy and ethoxy groups.

[0032] In formula (12), R is preferably an unsubstituted C1-C10 alkyl group, a C1-C10 alkyl group having a fluorine atom, a C1-C10 alkyl group having a cyano group, or an unsubstituted C6-C12 aryl group. For example, a methyl group, a phenyl group, a propyl group, etc., are preferred.

[0033] Furthermore, the polysilsesquioxane compound according to this embodiment has a structural unit represented by the above formula (1), R 1 and R 2 At least one of them may contain multiple different types of structural units.

[0034] The weight-average molecular weight of the polysilsesquioxane compound according to this embodiment can be appropriately set depending on the intended use, but is preferably 700 or more, particularly preferably 900 or more, and even more preferably 1200 or more. Furthermore, the weight-average molecular weight is preferably 20,000 or less, particularly preferably 15,000 or less, and even more preferably 10,000 or less. Having a weight-average molecular weight within the above range allows the curing reaction to proceed efficiently. In this specification, the weight-average molecular weight (Mw) is a value on a standard polystyrene basis measured by gel permeation chromatography (GPC), and the details of the measurement method are described in the test examples below.

[0035] The method for producing the polysilsesquioxane compound according to this embodiment is not particularly limited, but as mentioned above, it is preferable to produce it using a method that uses carbon dioxide as a material. For example, the method for producing the polysilsesquioxane compound according to this embodiment is: The following formula (2) [ka] (In the formula, R 1 R represents an alkylene group with 1 to 20 carbon atoms. 2 R represents an alkylene group with 1 to 10 carbon atoms. 3 (This represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms.) By reacting an epoxide having the structure shown with carbon dioxide, the following equation (3) is obtained. [ka] (In the formula, R 1 R represents an alkylene group with 1 to 20 carbon atoms. 2 R represents an alkylene group with 1 to 10 carbon atoms. 3 (This represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms.) Step (I) to obtain a compound having the structure shown, and Step (II): To obtain a polysilsesquioxane compound containing the structural unit shown in formula (1) above, by polycondensing a compound having the structure shown in formula (3) above. It is preferable to include it.

[0036] In equations (2) and (3) above, R 1 and R 2 The preferred option is the same as that explained above for equation (1). On the other hand, R in equation (3) above 3 As mentioned above, this is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, but the number of carbon atoms is particularly preferably 1 to 5, and more preferably 1 to 3. In particular, R 3 It is preferable that it be a methyl group.

[0037] The reaction between the epoxide and carbon dioxide in step (I) can be carried out by known methods. For example, the reaction can be carried out by stirring in a system in which the epoxide alone or a solvent in which the epoxide is dissolved is replaced with carbon dioxide gas. At this time, catalysts such as lithium bromide, tetrabutylammonium iodide, and pyridinemethanol may be added to the solvent. The temperature during stirring is preferably 15 to 80°C, particularly preferably 25 to 70°C, and even more preferably 40 to 60°C. Furthermore, the stirring time is preferably 12 to 96 hours, particularly preferably 24 to 96 hours, and even more preferably 36 to 96 hours. After the reaction, the compound shown in formula (3) can be separated from the solvent by appropriate extraction, washing, etc.

[0038] The polycondensation in step (II) can be carried out by known methods, for example, by a sol-gel reaction, such as a bulk polymerization method in which the reaction proceeds by adding only an aqueous hydrochloric acid solution to a compound having the structure shown in formula (3) above, or a solution polymerization method in which the reaction proceeds using an organic solvent. At this time, a polycondensation catalyst such as hydrochloric acid, phosphoric acid, or acetic acid may be added to the system. The temperature of the sol-gel reaction is preferably room temperature to 60°C, and the time is preferably 1 to 48 hours, particularly preferably 1 to 36 hours, and even more preferably 20 to 30 hours.

[0039] [Curable composition] As described above, the polysilsesquioxane compound according to this embodiment exhibits curability. Therefore, a curable composition exhibiting excellent curability can be obtained using the polysilsesquioxane compound according to this embodiment.

[0040] The curable composition according to this embodiment contains the polysilsesquioxane compound according to this embodiment, and may optionally contain other components. Examples of other components include silane coupling agents, fillers, amine compounds, and the like.

[0041] The amount of the polysilsesquioxane compound according to this embodiment in the curable composition according to this embodiment is preferably 1 to 30% by mass, particularly preferably 1 to 20% by mass, and even more preferably 1 to 10% by mass.

[0042] The curable composition according to this embodiment can be cured by heating. The heating conditions are set appropriately according to the composition of the curable composition, etc., but for example, heating at a temperature of 100 to 200°C is preferred, particularly heating at a temperature of 110 to 180°C, and even more preferably heating at a temperature of 120 to 150°C. The heating time is preferably 0.5 to 24 hours, particularly 1 to 20 hours, and even more preferably 2 to 15 hours.

[0043] By using the curable composition according to this embodiment, a cured product having a desired shape can be obtained. By forming the curable composition according to this embodiment into a sheet and curing it, a sheet-like cured product can be obtained. The cured product obtained by curing the curable composition according to this embodiment can be used for various applications, such as lenses, films, sealing materials, adhesives, bonding agents, films, protective films, and sealants.

[0044] Furthermore, an adhesive can be prepared using the curable composition according to this embodiment. This adhesive may contain the curable composition according to this embodiment alone, or it may contain the curable composition according to this embodiment and other components. This adhesive can be used in the same way as a general adhesive.

[0045] The embodiments described above are provided to facilitate understanding of the present invention and are not intended to limit it. Accordingly, each element disclosed in the above embodiments is intended to include all design modifications and equivalents that fall within the technical scope of the present invention. [Examples]

[0046] The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited to these examples.

[0047] [Example 1] 1. Preparation of alkoxysilanes having a cyclic carbonate group 100 parts by mass of 3-(methacryloyloxy)propyltrimethoxysilane and 2.2 parts by mass of lithium bromide were added to 400 parts by mass of N-N'-dimethylformamide, and the mixture was reacted at 50°C for 72 hours while stirring, with the system purged with carbon dioxide gas.

[0048] Next, ethyl acetate and purified water were added for extraction and washing. Furthermore, the organic layer was dried using anhydrous magnesium sulfate, the solid was filtered, and the ethyl acetate was removed by vacuum distillation to obtain a colorless, transparent liquid.

[0049] The resulting colorless, transparent liquid was treated as shown in Test Example 1 below. 1 1H NMR measurement and 13 When 13C NMR measurements were performed, and IR measurements were also performed as described in Test Example 2 below, the following equation (4) was obtained: [ka] It was confirmed that it is an alkoxysilane having the structure shown.

[0050] Note that Figures 1-3 show, 1 The results of the 1H NMR measurement are shown in Figure 4. 13The results of the 13C NMR measurement are shown, and the results of the IR measurement are shown in Figure 5. Here, Figures 2 and 3 are enlarged views of the regions enclosed by the dashed lines labeled A and B in Figure 1, respectively. In the NMR spectra shown in Figures 1 to 3, peaks originating from the hydrogen atoms located at a to g and g' of the alkoxysilane shown in Figure 1 could be confirmed. In addition, in the NMR spectrum shown in Figure 4, peaks originating from the carbon atoms located at 1 to 8 of the alkoxysilane shown in Figure 4 could be confirmed.

[0051] 2. Preparation of polysilsesquioxanes having cyclic carbonate groups 100 parts by mass of the alkoxysilane having the structure of formula (4) obtained in step 1 above was added to 10 parts by mass of a 1 M hydrochloric acid aqueous solution, and the sol-gel reaction was allowed to proceed at room temperature for 21 hours.

[0052] Subsequently, the product was extracted using methyl ethyl ketone, and the resulting organic layer was washed with an aqueous solution of sodium bicarbonate and purified water, and then dried using anhydrous magnesium sulfate. After filtering the solid, the methyl ethyl ketone was removed by distillation under reduced pressure to obtain a pale yellow viscous liquid.

[0053] The resulting pale yellow liquid was treated as shown in Test Example 1 below. 1 1H NMR measurement and 29 By performing Si NMR measurements and IR measurements as described in Test Example 2 below, the following equation (5) can be obtained. [ka] It was confirmed to be a polysilsesquioxane having the structure shown.

[0054] Figures 6 and 7 show, respectively 1 1H NMR measurement and 29The results of Si NMR measurements are shown. In the NMR spectrum shown in Figure 6, peaks originating from hydrogen atoms located at a~f and f' of polysilsesquioxane were observed. Furthermore, in the NMR spectrum shown in Figure 7, the positions of peaks originating from the three silicon atom structures (T structures; T1~T3) of polysilsesquioxane are shown. Here, the peak originating from T1 occurs around -48 ppm, the peak originating from T2 occurs around -57 ppm, and the peak originating from T3 occurs around -65 ppm. In terms of peak area proportion, the peak originating from T2 accounted for 22%, and the peak originating from T3 accounted for 78%.

[0055] Figure 8 shows the results of the IR measurement. The peaks in the figure indicate the peaks originating from the polysilsesquioxane region.

[0056] [Example 2] 1. Preparation of alkoxysilanes having a cyclic carbonate group 100 parts by mass of [8-(glycidoxy)n-octyl]trimethoxysilane and 2.2 parts by mass of lithium bromide were added to 400 parts by mass of N-N'-dimethylformamide, and the mixture was reacted at 50°C for 60 hours while stirring, with the system purged with carbon dioxide gas.

[0057] Next, ethyl acetate and purified water were added for extraction and washing. Furthermore, the organic layer was dried using anhydrous magnesium sulfate, the solid was filtered, and the ethyl acetate was removed by vacuum distillation to obtain a colorless liquid.

[0058] The resulting colorless liquid was treated as shown in Test Example 1 below. 1 1H NMR measurement and 13 When ¹ [ka] It was confirmed that it is an alkoxysilane having the structure shown.

[0059] Figures 9-12 show,1 The results of the 1H NMR measurement are shown in Figure 13. 13 The results of the 13C NMR measurement are shown, and the results of the IR measurement are shown in Figure 14. Here, Figures 10 to 12 show enlarged views of the regions enclosed by dashed lines labeled A to C in Figure 9. In the NMR spectra shown in Figures 10 to 12, peaks originating from the hydrogen atoms located a to i and i' of the alkoxysilane shown in Figure 9 could be confirmed. In addition, in the NMR spectrum shown in Figure 13, peaks originating from the carbon atoms located 1 to 13 of the alkoxysilane shown in Figure 13 could be confirmed.

[0060] 2. Preparation of polysilsesquioxanes having cyclic carbonate groups 100 parts by mass of the alkoxysilane having the structure of formula (7) obtained in step 1 above was added to 10 parts by mass of a 1 M hydrochloric acid aqueous solution, and the sol-gel reaction was allowed to proceed at room temperature for 21 hours.

[0061] Subsequently, the product was extracted using methyl ethyl ketone, and the resulting organic layer was washed with an aqueous solution of sodium bicarbonate and purified water, and then dried using anhydrous magnesium sulfate. After filtering the solid, the methyl ethyl ketone was removed by distillation under reduced pressure to obtain a colorless viscous liquid.

[0062] The obtained colorless viscous liquid was treated as shown in Test Example 1 below. 1 1H NMR measurement, and 29 By performing Si NMR measurements and IR measurements as described in Test Example 2 below, it was confirmed that in equation (1), R1 is a C8 alkylene group and R2 is a C1 alkylene group, resulting in a polysilsesquioxane.

[0063] Figure 15 shows the results of the IR measurement.

[0064] [Example 3] 100 parts by mass of alkoxysilane having the structure of formula (4) obtained in Example 1 and 49 parts by mass of methyltrimethoxysilane were mixed and then added to 14 parts by mass of 1M hydrochloric acid aqueous solution. The sol-gel reaction was allowed to proceed at room temperature, and gelation occurred after 21 hours. The resulting gel is expected to be a polysilsesquioxane having the basic structure shown in formula (8).

[0065] [ka]

[0066] [Example 4] 100 parts by mass of an alkoxysilane having the structure of formula (4), obtained in the same manner as in Example 1, and 71 parts by mass of trimethoxy(phenyl)silane were added to 13 parts by mass of a 1 M hydrochloric acid aqueous solution, and the sol-gel reaction was carried out at room temperature for 21 hours.

[0067] Subsequently, the product was extracted using methyl ethyl ketone, and the resulting organic layer was washed with an aqueous solution of sodium bicarbonate and purified water, and then dried using anhydrous magnesium sulfate. After filtering the solid, the methyl ethyl ketone was removed by distillation under reduced pressure to obtain a viscous liquid.

[0068] The obtained viscous liquid was treated as shown in Test Example 1 below. 1 1H NMR measurement and 29 By performing Si NMR measurements and IR measurements as described in Test Example 2 below, the following equation (9) can be obtained. [ka] It was confirmed to be a polysilsesquioxane with the basic structure of [the specified material].

[0069] Figures 16 and 17 show, respectively 1 1H NMR measurement and 29The results of Si NMR measurements are shown. In the NMR spectrum shown in Figure 16, peaks originating from carbon atoms located at positions a to g of polysilsesquioxane were confirmed. Furthermore, in the NMR spectrum shown in Figure 17, the positions of peaks originating from the four types of silicon atom structures of polysilsesquioxane (T structures; T2-R, T3-R, T2-Ph, T3-Ph; R is a group containing a cyclic carbonate group, Ph is a phenyl group) were shown. Here, the proportion of peak area was 27% for peaks originating from T2 and 73% for peaks originating from T3. Figure 18 shows the results of IR measurements.

[0070] [Example 5] 100 parts by mass of an alkoxysilane having the structure of formula (4), obtained in the same manner as in Example 1, and 58 parts by mass of trimethoxy(propyl)silane were added to 14 parts by mass of a 1 M hydrochloric acid aqueous solution, and the sol-gel reaction was carried out at room temperature for 21 hours.

[0071] Subsequently, the product was extracted using methyl ethyl ketone, and the resulting organic layer was washed with an aqueous solution of sodium bicarbonate and purified water, and then dried using anhydrous magnesium sulfate. After filtering the solid, the methyl ethyl ketone was removed by distillation under reduced pressure to obtain a viscous liquid.

[0072] The obtained viscous liquid was processed as shown in Test Example 1 below. 1 1H NMR measurement and 29 By performing Si NMR measurements and IR measurements as described in Test Example 2 below, the following equation (10) can be obtained. [ka] It was confirmed to be a polysilsesquioxane with the basic structure of [the specified material].

[0073] Figures 19 and 20 show, respectively 1 1H NMR measurement and 29The results of Si NMR measurements are shown. In the NMR spectrum shown in Figure 19, peaks originating from carbon atoms located at positions a~i,i' of polysilsesquioxane were confirmed. Furthermore, in the NMR spectrum shown in Figure 20, the positions of peaks originating from the three different silicon atom structures (T structures) of polysilsesquioxane are shown. Here, the proportion of peak area was 26% for peaks originating from T2 and 74% for peaks originating from T3. In addition, the results of IR measurements are shown in Figure 21.

[0074] [Example 6] 100 parts by mass of an alkoxysilane having the structure of formula (4), obtained in the same manner as in Example 1, and 122 parts by mass of an alkoxysilane having the structure of formula (7), obtained in the same manner as in Example 2, were added to 10 parts by mass of a 1 M hydrochloric acid aqueous solution, and the sol-gel reaction was allowed to proceed at room temperature for 21 hours.

[0075] Subsequently, the product was extracted using methyl ethyl ketone, and the resulting organic layer was washed with an aqueous solution of sodium bicarbonate and purified water, and then dried using anhydrous magnesium sulfate. After filtering the solid, the methyl ethyl ketone was removed by distillation under reduced pressure to obtain a viscous liquid.

[0076] The obtained viscous liquid was processed as shown in Test Example 1 below. 1 1H NMR measurement and 29 By performing Si NMR measurements and IR measurements as described in Test Example 2 below, the following equation (11) can be obtained. [ka] It was confirmed to be a polysilsesquioxane with the basic structure of [the specified material].

[0077] Figures 22 and 23 show, respectively 1 1H NMR measurement and 29The results of Si NMR measurements are shown. In the NMR spectrum shown in Figure 22, peaks originating from carbon atoms located at a~n and n' in polysilsesquioxane were observed. Furthermore, in the NMR spectrum shown in Figure 23, the positions of peaks originating from the three different silicon atom structures (T structures) of polysilsesquioxane are shown. Here, the proportion of peak area was 3% for peaks originating from T1, 50% for peaks originating from T2, and 47% for peaks originating from T3. Figure 24 shows the results of IR measurements.

[0078] [Test Example 1] (NMR Measurement) (1) 1 H-NMR measurement Under the following conditions 1 1H-NMR measurements were performed. Equipment: Bruker, product name "Biospin Avance 500") 1 H-NMR resonance frequency: 500MHz Probe: 5mmφ solution probe Measurement temperature: room temperature (25℃) Repeat time: 1s Total number of times: 16

[0079] 1 The samples for H-NMR measurement were prepared under the following conditions. Silane compound concentration: 3% Measurement solvent: CDCl3 or DMSO-d6

[0080] (2) 29 Si-NMR measurement Under the following conditions 29 Si-NMR measurements were performed. Device: Bruker BioSpin, product name "AV-500" 29Si-NMR resonance frequency: 99.352MHz Probe: 5mmφ solution probe Measurement temperature: room temperature (25℃) Sample rotation speed: 20kHz Measurement method: Inverse gate decoupling method 29Si Flip angle: 90° 29Si 90° pulse width: 8.0 μs Repeat time: 5s Total number of times: 9200 Observation range: 30kHz

[0081] 29 The samples for Si-NMR measurement were prepared under the following conditions. In order to shorten the relaxation time, Fe(acac)3 was added as a relaxation reagent during the measurement. Polysilsesquioxane compound concentration: 30% by mass Fe(acac)3 concentration: 0.7% by mass Measurement solvent: Deuterated acetone Internal standard: TMS

[0082] (3) 13 C-NMR measurement Under the following conditions 13 1C-NMR measurements were performed. Equipment: Bruker, product name "Biospin Avance 500") 1 H-NMR resonance frequency: 500MHz Probe: 5mmφ solution probe Measurement temperature: room temperature (25℃) Repeat time: 1s Total number of times: 1024

[0083] 13 The samples for 1C-NMR measurement were prepared under the following conditions. Silane compound concentration: 3% Measurement solvent: CDCl3 or DMSO-d6

[0084] [Test Example 2] (IR Measurement) The IR spectrum was obtained using a Fourier transform infrared spectrophotometer (PerkinElmer Spectrum100) at wavenumbers 4000–400 cm⁻¹. -1 Measurements were taken within the specified range.

[0085] [Test Example 3] (GPC measurement) The mass-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polysilsesquioxanes obtained in Examples 1-2 and 4-6 were measured using the following apparatus and conditions, converted to standard polystyrene equivalents. The results are shown in Table 1. Device name: HLC-8220GPC (manufactured by Tosoh Corporation) Column: A sequential concatenation of TSKgelGMHXL, TSKgelGMHXL, and TSKgel2000HXL. Solvent: tetrahydrofuran Injection volume: 20μl Measurement temperature: 40℃ Flow rate: 1ml / min Detector: Differential refractometer

[0086] [Test Example 4] (Shear Strength Measurement) Polysilsesquioxane (curable composition) obtained in Examples 1, 4, 5, and 6 was applied to a SUS304 plate (manufactured by Paltec Co., Ltd.; 35 mm x 100 mm) over an area of ​​35 mm x 10 mm. Another SUS304 plate (35 mm x 10 mm) was then placed on top of the applied surface and pressed together.

[0087] Subsequently, the material was hardened by heat treatment at 150°C. The heating time was 2 hours or 15 hours, as shown in Table 1. After that, the shear strength (N) was measured using an Autograph (Shimadzu Corporation, product name "AG-X Puls") at a shear rate of 10 mm / min. The results are shown in Table 1.

[0088] Furthermore, the polysilsesquioxane obtained in Example 2 gelled after 2 days of storage at room temperature, so shear strength measurements were not performed. Similarly, the gelled polysilsesquioxane obtained in Example 3 also did not undergo shear strength measurements. Moreover, for the same reasons, the following thermogravimetric analysis was not performed on the polysilsesquioxane obtained in Examples 2 and 3.

[0089] [Test Example 5] (Measurement of thermogravimetric loss) The polysilsesquioxanes obtained in Examples 1 and 4-6 were analyzed using a thermogravimetric analyzer (TGA; Shimadzu Corporation, product name "DTA-60") in an air atmosphere at a heating rate of 5°C / min in the range of 40°C to 550°C, and the 5% weight loss temperature (T) was determined. d5 The temperature (°C) was measured. The results are shown in Table 1 as the 5% weight loss temperature for the "pre-curing" state.

[0090] Furthermore, the polysilsesquioxanes obtained in Examples 1 and 4-6, which were thermocured in the same manner as in Test Example 4, also had a 5% weight loss temperature (T) similar to the above. d5 The temperature (°C) was measured. The results are shown in Table 1 as the 5% weight loss temperature "after curing".

[0091] [Table 1] [Industrial applicability]

[0092] The polysilsesquioxane compound of the present invention has sufficient shear strength after curing and also has a high 5% weight loss temperature, making it suitable for use as a material in curable compositions used in applications where the material is exposed to high temperatures for extended periods (for example, compositions for fixing optical elements).

Claims

1. The following formula (1) 【Chemistry 1】 (In the formula, R １ R represents an alkylene group with 1 to 20 carbon atoms. ２ (This represents an alkylene group with 1 to 10 carbon atoms.) A polysilsesquioxane compound characterized by containing the structural unit shown by .

2. The polysilsesquioxane compound according to claim 1, characterized in that the weight-average molecular weight is 700 or more and 20,000 or less.

3. The aforementioned R ２ The polysilsesquioxane compound according to claim 1, characterized in that it is a methylene group.

4. A curable composition characterized by containing a polysilsesquioxane compound according to any one of claims 1 to 3.

5. A cured product characterized by being obtained by curing the curable composition described in claim 4.

6. An adhesive containing the curable composition described in claim 4.

7. A method for producing a polysilsesquioxane compound according to any one of claims 1 to 3, The following formula (2) 【Chemistry 2】 (In the formula, R １ R represents an alkylene group with 1 to 20 carbon atoms. ２ R represents an alkylene group with 1 to 10 carbon atoms. ３ (This represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) By reacting an epoxide having the structure shown with carbon dioxide, the following equation (3) is obtained. 【Transformation 3】 (wherein, R １ represents an alkylene group having 1 to 20 carbon atoms, and R ２ represents an alkylene group having 1 to 10 carbon atoms, and R ３ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) Step (I) to obtain a compound having the structure shown, and Step (II) to obtain a polysilsesquioxane compound containing the structural unit shown in formula (1) by polycondensing a compound having the structure shown in formula (3). A manufacturing method characterized by including the following.

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