Curable compositions, cured products, and adhesives

Abstract

The present invention provides a curable composition having excellent curability and useful in reducing carbon dioxide emissions, a cured product obtained by curing the curable composition, and an adhesive containing the curable composition. [Solution] A curable composition containing a cyclic carbonate group-containing siloxane compound and an amino group-containing compound.

Description

[Technical Field]

[0001] The present invention relates to a curable composition containing a novel cyclic carbonate group-containing siloxane compound, a cured product obtained by curing the curable composition, and an adhesive containing the curable composition. [Background technology]

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

[0003] Optical devices include various types of lasers such as semiconductor lasers (LDs), light-emitting elements such as light-emitting diodes (LEDs), photodetectors, composite optical devices, and optical integrated circuits. In recent years, optical devices that emit blue light and white light, which have shorter peak wavelengths, have been developed and are widely used. The brightness of these light-emitting elements with shorter peak wavelengths has increased dramatically, and consequently, the amount of heat generated by these optical devices tends to increase even further.

[0004] However, with the increasing brightness of optical elements in recent years, a problem has arisen where the cured product of the optical element fixing agent is exposed to higher energy light and higher temperatures generated by the optical element for extended periods, causing it to deteriorate and peel off.

[0005] To solve this problem, Patent Documents 1 to 3 propose compositions for fixing photonic devices, in which polysilsesquioxane compounds are the main component.

[0006] Polysilsesquioxane compounds are composed of inorganic silica [SiO2] and organosilicone [(R2SiO)]. n It is an intermediate substance of ], and its formula is: (RSiO 3 / 2 ) n The compound is represented by the formula (wherein R may have substituents, such as an alkyl group or aryl group).

[0007] Polysilsesquioxane compounds have siloxane bonds (bonds between silicon atoms and oxygen atoms) as described above. As other compounds having siloxane bonds, cyclic siloxane compounds are also known. A cyclic siloxane compound refers to a cyclic organic compound having a cyclic molecular structure skeleton formed by siloxane bonds. In Patent Documents 4 and 5, inventions related to cyclic siloxane compounds are disclosed.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0009] By the way, in recent years, with the increasing voices calling for the construction of a recycling-oriented society, gases such as carbon dioxide, methane, and carbon monoxide have attracted attention as sustainable carbon raw materials. For example, it has been reported that an aliphatic polycarbonate having only aliphatic (non-aromatic) groups in the main chain can be produced by copolymerizing carbon dioxide and an epoxide, and there is interest in chemical products using gases such as carbon dioxide as raw materials and their manufacturing technologies. Since carbon dioxide is considered a cause of global warming, the effective utilization of carbon dioxide discharged from factories in the process of making various materials is helpful for environmental protection.

[0010] This invention has been made in view of the above circumstances, and aims to provide a curable composition that has excellent curability and is also useful in reducing carbon dioxide emissions, a cured product obtained by curing the curable composition, and an adhesive containing the curable composition. [Means for solving the problem]

[0011] To achieve the above objective, firstly, the present invention provides a curable composition characterized by containing a cyclic carbonate group-containing siloxane compound and an amino group-containing compound (Invention 1).

[0012] In the above invention (Invention 1), the cyclic carbonate group-containing siloxane compound is defined by the following formula (1) [ka] (In the formula, R 1 R represents an alkylene group with 1 to 20 carbon atoms. 2 represents an alkylene group with 1 to 10 carbon atoms. ) Polysilsesquioxane compounds containing the structural unit shown by ), and the following formula (2) [ka] (In the formula, n represents an integer from 1 to 6, m represents an integer from 0 to 5, the sum of n and m is an integer from 3 to 6, the order of existence of the units enclosed in parentheses with n and m is arbitrary in formula (2), R 3 R represents an alkylene group with 1 to 20 carbon atoms. 4 R represents an alkylene group with 1 to 10 carbon atoms. 5 (wherein represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) Preferably, it is at least one selected from cyclic siloxane compounds having the structure shown (Invention 2).

[0013] In the above inventions (Inventions 1 and 2), the amino group-containing compound is preferably a compound having two or more amino groups in one molecule (Invention 3).

[0014] In the above inventions (Inventions 1 to 3), the content of the amino group-containing compound in the curable composition is preferably 1 part by mass or more and 80 parts by mass or less per 100 parts by mass of the cyclic carbonate group-containing siloxane compound (Invention 4).

[0015] In the above invention (Invention 2), the weight-average molecular weight of the polysilsesquioxane compound is preferably 700 or more and 20,000 or less (Invention 5).

[0016] Secondly, the present invention provides a cured product characterized by being obtained by curing the curable composition (Inventions 1 to 5) (Invention 6).

[0017] Thirdly, the present invention provides an adhesive containing the curable composition (Inventions 1 to 5) (Invention 7). [Effects of the Invention]

[0018] The curable composition according to the present invention has excellent curability and is also useful in reducing carbon dioxide emissions. [Modes for carrying out the invention]

[0019] Embodiments of the present invention will be described below. The curable composition according to this embodiment contains a cyclic carbonate group-containing siloxane compound and an amino group-containing compound.

[0020] The cyclic carbonate group-containing siloxane compound in this embodiment contains a cyclic carbonate group. That is, the cyclic carbonate group-containing siloxane compound in this embodiment has the following formula (3) in its molecule [ka] It has a cyclic carbonate group represented by (4). When the curable composition according to this embodiment is heated, the following formula (4) is formed between the cyclic carbonate group and the amino group of the amino group-containing compound. [Chemical formula] The reaction represented by the following occurs. Specifically, the cyclic carbonate group selectively reacts with the amino group of the amino group-containing compound, and the cyclic carbonate group undergoes ring-opening to form a urethane bond having a hydroxyl group. The cyclic carbonate group-containing siloxane compound has a plurality of cyclic carbonate groups in one molecule, and as a result of the above reaction occurring in each of them, the curable composition hardens strongly and rapidly. Specifically, an organic-inorganic hybrid type polyurethane having a hydroxyl group, that is, an organic-inorganic hybrid type poly(hydroxyurethane) is obtained by the ring-opening polyaddition reaction of the cyclic carbonate group-containing siloxane compound and the amino group-containing compound. Therefore, the curable composition according to the present embodiment exhibits excellent heat resistance, flexibility, and adhesiveness. Further, since dipole interaction also occurs between the cyclic carbonate groups in the cyclic carbonate group-containing siloxane compound, connection between the cyclic carbonate group-containing siloxane compounds without an amino group-containing compound also occurs, which also contributes to the curing of the curable composition. As a result of the above, the curable composition according to the present embodiment exhibits excellent curability, heat resistance, flexibility, and adhesiveness.

[0021] Also, as described later, when producing the cyclic carbonate group-containing siloxane compounds according to the present embodiment, carbon dioxide can be used as one of the materials. Therefore, the curable composition according to the present embodiment is useful for reducing carbon dioxide emissions from the viewpoint of carbon neutrality.

[0022] 1. Cyclic carbonate group-containing siloxane compound The cyclic carbonate group-containing siloxane compound in the present embodiment is not particularly limited as long as it is a siloxane compound containing a cyclic carbonate group in the molecule, but preferably the following formula (1) [Chemical formula] (In the formula, R 1R represents an alkylene group with 1 to 20 carbon atoms. 2 (This represents an alkylene group with 1 to 10 carbon atoms.) Polysilsesquioxane compounds containing the structural unit shown, and The following formula (2) [ka] (In the formula, n represents an integer from 1 to 6, m represents an integer from 0 to 5, the sum of n and m is an integer from 3 to 6, the order of existence of the units enclosed in parentheses with n and m is arbitrary in formula (2), R 3 R represents an alkylene group with 1 to 20 carbon atoms. 4 R represents an alkylene group with 1 to 10 carbon atoms. 5 (This represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms.) Cyclic siloxane compounds having the structure shown Preferably, it is at least one selected from the following.

[0023] (1) Polysilsesquioxane compounds As described above, the polysilsesquioxane compound in 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 by .

[0024] In the structure shown in formula (1) above, R 1 As mentioned 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. In particular, R 1 It is preferable that it is a propylene group.

[0025] Furthermore, in the structure shown in formula (1) above, R2 As 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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 makes the curable composition according to this embodiment easier to cure. Note that the weight-average molecular weight (Mw) in this specification is a value on a standard polystyrene basis measured by gel permeation chromatography (GPC), and the details of the measurement method are as described in the test examples below.

[0037] 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 (5) [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. 6 (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 (6) 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. 6 (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 (6) above. It is preferable that it includes.

[0038] In equations (5) and (6) above, R 1 and R 2 The preferred option for is the same as that explained above for equation (1). On the other hand, R 6 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 6 It is preferable that it be a methyl group.

[0039] 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 stirring temperature is preferably 15 to 80°C, more preferably 25 to 70°C, and even more preferably 40 to 60°C. Furthermore, the stirring time is preferably 12 to 96 hours, more preferably 24 to 96 hours, and even more preferably 36 to 96 hours. After the reaction, the compound shown in formula (6) can be separated from the solvent by appropriate extraction, washing, etc.

[0040] 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 an aqueous hydrochloric acid solution to a compound having the structure shown in formula (6) 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.

[0041] (2) Cyclic siloxane compounds As described above, the cyclic siloxane compound in this embodiment is given by the following formula (2) [ka] (In the formula, n represents an integer from 1 to 6, m represents an integer from 0 to 5, the sum of n and m is an integer from 3 to 6, the order of existence of the units enclosed in parentheses with n and m is arbitrary in formula (2), R 3 R represents an alkylene group with 1 to 20 carbon atoms. 4R represents an alkylene group with 1 to 10 carbon atoms. 5 (This represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms.) It has the structure shown in [image / diagram].

[0042] In the structure shown in formula (2) above, the sum of n and m represents an integer from 3 to 6, as described above, but it is particularly preferable that the integer is from 3 to 5, and even more preferably from 3 to 4. As described above, n is an integer from 1 to 6, and m is an integer from 0 to 5, as described above, but from the viewpoint of easily achieving good curability, it is preferable that n is an integer greater than m, and from the same viewpoint, it is preferable that m is 0 (i.e., all units constituting the cyclic siloxane compound are units to which n is attached in formula (1) above).

[0043] In the structure shown in formula (2) above, R 3 As mentioned 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. In particular, R 3 It is preferable that it is a propylene group.

[0044] Furthermore, in the structure shown in formula (2) above, R 4 As 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 4 It is preferable that it is a methylene group.

[0045] Furthermore, in the structure shown in formula (2) above, R 5 As described 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 5 It is preferable that it be a methyl group.

[0046] The method for producing the cyclic siloxane 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 cyclic siloxane compound according to this embodiment is: The following formula (7) [ka] (In the formula, x represents an integer between 3 and 6, R 3 R represents an alkylene group with 1 to 20 carbon atoms. 4 R represents an alkylene group with 1 to 10 carbon atoms. 5 (This represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms.) A step to obtain a compound having the structure shown in formula (2) above by reacting an epoxy group-containing cyclic siloxane compound having the structure shown with carbon dioxide. It is preferable that it includes.

[0047] In the above equation (7), R 3 , R 4 and R 5 The preferred options for are the same as those described above for equation (2). Also, as mentioned above, x represents an integer between 3 and 6, but it is particularly preferable that the integer be between 3 and 5, and even more preferably between 3 and 4.

[0048] The reaction between the epoxy group-containing cyclic siloxane compound and carbon dioxide in the above step can be carried out by known methods. For example, the reaction can be carried out by stirring in a system in which the solvent containing the epoxy group-containing cyclic siloxane compound is dissolved and replaced with carbon dioxide gas. At this time, catalysts such as lithium bromide, tetrabutylammonium iodide, and pyridinemethanol may be added to the solvent. The stirring temperature 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 (2) can be separated from the solvent by appropriate extraction, washing, etc.

[0049] 2. Amino group-containing compounds The amino group-containing compound in this embodiment is not particularly limited as long as it is a compound containing an amino group. From the viewpoint of ensuring that the curable composition according to this embodiment hardens efficiently, the amino group-containing compound is preferably a compound having one or more amino groups in one molecule, and is particularly likely to be a compound having one or more amino groups in one molecule. 2 It is preferable that the compound has 10 or more amino groups. The upper limit of the number of amino groups in an amino group-containing compound is not particularly limited, but for example, it is preferable that there are 10 or fewer amino groups per molecule, more preferably 5 or fewer amino groups per molecule, particularly preferably 3 or fewer amino groups per molecule, and even more preferably 2 amino groups per molecule.

[0050] Preferred examples of amino group-containing compounds in this embodiment include diamine compounds and triamine compounds, with diamine compounds being particularly preferred. The amino group-containing compound in this embodiment may also be an amine compound having a cyclic structure. Furthermore, from the viewpoint of further improving reactivity and curability, an amino group having a nitrogen-hydrogen bond is preferred as the amino group, at least one amino group selected from the group consisting of primary amino groups and secondary amino groups is more preferred, and a primary amino group is even more preferred.

[0051] Examples of diamine compounds include ethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, N-isopropylethylenediamine, N,N'-dimethylethylenediamine, 1,3-diaminopropane, N,N'-dimethyl-1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 2,2-dimethyl-1,3-diaminopropane, 1,6-diaminohexane, 1,8-diaminooctane, 1,12-diaminododecane, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), di Examples include minocyclohexane, isophoronediamine, 4,4'-bipiperidine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, 3-aminopyrrolidine, 3-aminopiperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 1,2-dianilinoethane, phenylenediamine, tollidine, 2,2',6,6'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, diethyltoluenediamine, and 4,4'-bis(sec-butylamino)diphenylmethane. Among these, 1,4-diaminobutane is preferred from the viewpoint of ensuring that the curable composition according to this embodiment hardens well.

[0052] Examples of triamine compounds include diethylenetriamine, spermidine, 2,4,6-trimethyltriazine, 1,4,7-triazacyclononane, and 1,5,9-triazacyclododecene.

[0053] The content of the amino group-containing compound in the curable composition according to this embodiment is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and more preferably 8 parts by mass or more, per 100 parts by mass of the cyclic carbonate group-containing siloxane compound. Furthermore, the above content is preferably 80 parts by mass or less, more preferably 65 parts by mass or less, and more preferably 45 parts by mass or less, per 100 parts by mass of the cyclic carbonate group-containing siloxane compound. When the content of the amino group-containing compound is within the above range, the curable composition according to this embodiment is more likely to cure well.

[0054] 3. Preparation of curable composition The curable composition according to this embodiment is not particularly limited and can be obtained, for example, by mixing the aforementioned cyclic carbonate group-containing siloxane compound and the aforementioned amino group-containing compound in a desired ratio.

[0055] The above mixing may be carried out in a desired solvent, in which case the curable composition according to this embodiment can be prepared in the form of a coating liquid. Even without using a solvent, the curable composition according to this embodiment can be prepared in the form of a coating liquid depending on the properties of the materials. In addition, the curable composition according to this embodiment may contain other components besides the cyclic carbonate group-containing siloxane compound and the amino group-containing compound. Examples of other components include fillers, modifying components such as plasticizers, flow adjusting components such as thixotropes, pigments, leveling agents, tackifiers, elastomer fine particles, curing accelerators, foam stabilizers, and chemical blowing agents.

[0056] 4. Use of curable composition As described above, the curable composition according to this embodiment exhibits excellent curability. Therefore, 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 in a variety of applications, such as lenses, films, sealing materials, adhesives, bonding agents, films, protective films, sealants, die bonding materials for semiconductors, and compositions for fixing optical elements.

[0057] 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.

[0058] The heating conditions for curing the curable composition or adhesive according to this embodiment are set appropriately according to the composition of the curable composition, etc., but for example, heating at a temperature of 25 to 250°C is preferred, heating at a temperature of 30 to 150°C is particularly preferred, and heating at a temperature of 50 to 100°C is even more preferred. The heating time is preferably 30 minutes to 24 hours, particularly 1 hour to 20 hours, and even more preferably 2 hours to 15 hours.

[0059] 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]

[0060] 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.

[0061] [Synthesis Example 1] (Polysilsesquioxane compound) 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.

[0062] 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 pale yellow liquid.

[0063] Regarding the pale yellow liquid obtained, 1 H NMR measurement, 13 ¹¹C NMR and IR measurements were performed, and the following equation (8) was obtained: [ka] It was confirmed that it is an alkoxysilane having the structure shown.

[0064] 2. Preparation of polysilsesquioxanes having cyclic carbonate groups 100 parts by mass of the alkoxysilane having the structure of formula (8) 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.

[0065] 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.

[0066] Regarding the pale yellow liquid obtained, 1 1H NMR measurement and 29By performing Si NMR measurements and IR measurements, the following equation (9) is obtained. [ka] It was confirmed to be a polysilsesquioxane having the structure shown.

[0067] Furthermore, the mass-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the above polysilsesquioxane were measured as standard polystyrene equivalent values ​​by gel permeation chromatography (GPC) under the following conditions, and were found to be 2510 and 1.36, respectively.

[0068] [GPC method] 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

[0069] [Synthesis Example 2] (Cyclic Siloxane Compound) The following formula (10) [ka] 100 parts by mass of methylpropylglycidyl cyclic siloxane having the structure shown and 2.8 parts by mass of lithium bromide were added to 150 parts by mass of N-N'-dimethylformamide, and the mixture was reacted at 50°C for 72 hours while stirring under conditions of carbon dioxide gas purging. The compound of formula (10) is the same as the compound of formula (7) described above, where x is 4 and R 1 is an n-propylene group, R 2 The methylene group is R 3 This corresponds to a compound in which the atom is a hydrogen atom.

[0070] Subsequently, ethyl acetate and purified water were added to extract the organic layer, and the resulting organic layer was washed with purified water. The washed organic layer was then dried using anhydrous magnesium sulfate. After that, the anhydrous magnesium sulfate was filtered, and the ethyl acetate was removed by vacuum distillation to obtain a pale yellow liquid.

[0071] Regarding the pale yellow liquid obtained, 1 1H NMR measurement and 13 By performing 13C NMR measurements, IR measurements, and LC-MS measurements, the following equation (11) is obtained. [ka] It was confirmed that the compound is a cyclic siloxane compound having a cyclic carbonate group with the structure shown. In particular, LC-MS measurement revealed that only a peak at m / z 895.2328 was observed, confirming that this matches the molecular weight of a cyclic siloxane compound having a cyclic carbonate group with the structure of formula (11) with sodium ions added. Note that in formula (2) above, n is 4, m is 0, and R 1 is an n-propylene group, R 2 The methylene group is R 3 This corresponds to a compound in which the atom is a hydrogen atom.

[0072] Furthermore, the analysis confirmed that in the cyclic siloxane compound, all of the epoxy groups in formula (10) used as the material were replaced with cyclic carbonate groups.

[0073] [Example 1] A coating solution for a curable composition was obtained by mixing 100 parts by mass of the cyclic siloxane compound obtained in Synthesis Example 2 as a cyclic carbonate group-containing siloxane compound with 42 parts by mass of 1,4-diaminobutane as an amino group-containing compound.

[0074] [Examples 2-4] A curable composition was obtained in the same manner as in Example 1, except that the mass ratio was changed as shown in Table 1.

[0075] [Test Example 1] (Measurement of Shear Strength) Two SUS304 substrates, each 70 mm long, 10 mm wide, and 0.1 mm thick, were prepared. On one side of one of the substrates, the coating solution obtained in the example was applied to one of the two equal areas (a 35 mm x 10 mm area) so that the thickness after curing would be 100 μm.

[0076] The other substrate was laminated onto the obtained coating film. At this time, one of the two equal parts of the substrate (a 35mm x 10mm area) was in contact with the coating film, and the two substrates were laminated so that they overlapped only in the area covered by the coating film.

[0077] The resulting laminate was heated at 50°C for 12 hours to cure the coating of the curable composition, resulting in a cured product. This yielded a test specimen for measuring shear strength.

[0078] Then, using an Autograph (manufactured by Shimadzu Corporation, product name "AG-X Puls"), with one substrate of the test specimen fixed, a force was applied to the other substrate at a speed of 10 mm / min in a direction parallel to the long side of the substrate. The maximum force (N) at which the cured material broke or peeled off from one of the substrates was measured and defined as the shear strength. The results are shown in Table 1.

[0079] [Table 1]

[0080] As can be seen from Table 1, the curable compositions obtained in the examples cured well upon heating and exhibited sufficient shear strength. This indicates that the curable compositions according to this embodiment can be used as excellent cured products and adhesives. [Industrial applicability]

[0081] The curable composition of the present invention can be suitably used as a cured product or an adhesive.

Claims

1. A curable composition characterized by containing a cyclic carbonate group-containing siloxane compound and an amino group-containing compound.

2. The cyclic carbonate group-containing siloxane compound is given by 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.) Polysilsesquioxane compounds containing the structural unit shown, and The following formula (2) 【Chemistry 2】 (In the formula, n represents an integer from 1 to 6, m represents an integer from 0 to 5, the sum of n and m is an integer from 3 to 6, the order of existence of the units enclosed in parentheses with n and m is arbitrary in formula (2), R ３ R represents an alkylene group with 1 to 20 carbon atoms. ４ R represents an alkylene group with 1 to 10 carbon atoms. ５ (This represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) Cyclic siloxane compounds having the structure shown The curable composition according to claim 1, characterized in that it is at least one selected from the following.

3. The curable composition according to claim 1, characterized in that the amino group-containing compound is a compound having two or more amino groups in one molecule.

4. The curable composition according to claim 1, characterized in that the content of the amino group-containing compound in the curable composition is 1 part by mass or more and 80 parts by mass or less per 100 parts by mass of the cyclic carbonate group-containing siloxane compound.

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

6. A cured product characterized by being obtained by curing the curable composition described in claim 1.

7. An adhesive containing the curable composition described in claim 1.

Images