Thermally cationic polymerizable composition, use of the same, cationic polymerization process using the same, and stabilizer for thermally cationic polymerizable compositions

Abstract

A thermally cationically polymerizable composition is provided, comprising a cationically polymerizable compound (A), a cationic polymerization initiator (B), and a stabilizer (C), represented by formula (2) shown below, wherein the thermally cationically polymerizable composition comprises 0.01 to 20 parts by mass of the cationic polymerization initiator (B) per 100 parts by mass of the cationically polymerizable compound (A) and comprises 0.1 to 50 parts by mass of the stabilizer (C) per 100 parts by mass of the cationic polymerization initiator (B). In formula (2), R 4 , R 5 and R 6Each independently comprises an alkyl group with 1 to 10 carbon atoms, optionally containing a substituent, an aryl group with 6 to 15 carbon atoms, optionally containing a substituent, or an aralkyl group with 7 to 15 carbon atoms, optionally containing a substituent. This configuration provides a thermally cationically polymerizable composition with a long pot life despite the use of a cationic polymerization initiator with a low polymerization initiation temperature.

Description

Technical field

[0001] The present invention relates to a thermally cationically polymerizable composition in which cationic polymerization occurs upon heating, and to its use. The present invention also relates to a cationic polymerization process in which the thermally cationically polymerizable composition is used. Furthermore, the present invention relates to a stabilizer for a thermally cationically polymerizable composition. State of the art

[0002] Accelerating cationic polymerization by heating a cationically polymerizable composition containing a cationically polymerizable compound and a cationic polymerization initiator is a common practice. For example, a cured epoxy resin can be obtained by mixing a cationic polymerization initiator with an epoxy compound in liquid form and then heating the mixture. Such an epoxy resin is widely used for various applications, including bonding and encapsulating electronic components.

[0003] Onium salts, typically sulfonium salts, are commonly used as cationic polymerization initiators. The anionic species that may be present in the onium salts are preferably those derived from a superstrong acid, such as tetrakis(pentafluorophenyl)borate and hexafluoroantimonate, thus successfully achieving a lower initiation temperature for cationic polymerization. A lower polymerization initiation temperature is advantageous, for example, for inhibiting shrinkage after curing, protecting electronic components, and reducing energy consumption. However, cationically polymerizable compositions with a low polymerization initiation temperature can cause cationic polymerization to progress during storage and consequently exhibit the problem of a short pot life.For this reason, in some cases a stabilizer is used to inhibit the progression of cationic polymerization during storage.

[0004] For example, patent document 1 describes a stabilization process for an alicyclic epoxy resin, wherein a combination of a sulfonium salt containing methyl sulfate or ethyl sulfate as an anionic species and an aromatic sulfide, the combination serving as a stabilizer, is mixed with an alicyclic epoxy resin containing a sulfonium salt containing hexafluoroantimonate, hexafluorophosphate, tetrakis(pentafluorophenyl)borate, or the like as an anionic species, the sulfonium salt serving as a polymerization initiator. However, the stabilization effect remains insufficient, and achieving a long pot life is often difficult.

[0005] Furthermore, patent document 2 describes the use of a sulfonium salt containing trifluoromethanesulfonate as an anionic species as a polymerization initiator. However, this polymerization initiator has a problem with a high polymerization initiation temperature. Document listPatent documents Patent Document 1: JP 2019-189698 A Patent Document 2: JP 2004-217551 A Summary of the invention: Technical problem

[0006] The present invention was developed to solve the aforementioned problems, and one object of the present invention is to provide a thermally cationically polymerizable composition with a long pot life despite the use of a cationic polymerization initiator with a low polymerization initiation temperature, and to provide such a composition. Another object of the present invention is to provide a cationic polymerization process using the thermally cationically polymerizable composition. Furthermore, a further object of the present invention is to provide a stabilizer for a thermally cationically polymerizable composition with a long pot life. Solution to the problem

[0007] The above problems are solved by providing a thermally cationically polymerizable composition comprising a cationically polymerizable compound (A), a cationic polymerization initiator (B) represented by formula (1) shown below, and a stabilizer (C) represented by formula (2) shown below, wherein The thermally cationically polymerizable composition comprises 0.01 to 20 parts by mass of the cationic polymerization initiator (B) per 100 parts by mass of the cationically polymerizable compound (A) and 0.1 to 50 parts by mass of the stabilizer (C) per 100 parts by mass of the cationic polymerization initiator (B).

[0008] In formula (1) R 1 , R 2 and R 3each independently an alkyl group with 1 to 10 carbon atoms, optionally having a substituent, an aryl group with 6 to 15 carbon atoms, optionally having a substituent, or an aralkyl group with 7 to 15 carbon atoms, optionally having a substituent; X is B(R f 1 )4, Sb(R f 2 )6, P(R f 3 )6, N(R f 4 )2, C(R f 5 )3, Al(R f 6 )4 or Ga(R f 7 )4, where R f 1 to R f 7Each independently comprises a fluorine-containing group selected from the group consisting of a fluorine atom, a perfluoroalkyl group with 1 to 6 carbon atoms, a perfluoroaryl group with 6 to 10 carbon atoms, a perfluoroalkyl-substituted aryl group with 7 to 14 carbon atoms, a perfluoroalkylsulfonyl group with 1 to 6 carbon atoms, and a perfluoroalkoxy group with 1 to 6 carbon atoms; and several perfluoroalkyl groups, perfluoroalkylsulfonyl groups, or perfluoroalkoxy groups are optionally linked together to form a ring.

[0009] In formula (2) R 4 , R 5 and R 6each independently an alkyl group with 1 to 10 carbon atoms, optionally having a substituent, an aryl group with 6 to 15 carbon atoms, optionally having a substituent, or an aralkyl group with 7 to 15 carbon atoms, optionally having a substituent.

[0010] It is preferred that in formula (1) R f 1 a fluorine atom, a perfluoroaryl group with 6 to 10 carbon atoms, a perfluoroalkyl-substituted aryl group with 7 to 14 carbon atoms, or a perfluoroalkoxy group with 1 to 6 carbon atoms; R f 2 a fluorine atom; R f 3 a fluorine atom or a perfluoroalkyl group with 1 to 6 carbon atoms; R f 4 a perfluoroalkylsulfonyl group with 1 to 6 carbon atoms; R f 5a perfluoroalkylsulfonyl group with 1 to 6 carbon atoms; R f 6 a perfluoroalkoxy group with 1 to 6 carbon atoms; and R f 7 a fluorine atom, a perfluoroalkyl group with 1 to 6 carbon atoms, a perfluoroaryl group with 6 to 10 carbon atoms, or a perfluoroalkyl-substituted aryl group with 7 to 14 carbon atoms.

[0011] The thermally cationically polymerizable composition in each of the configurations can comprise 0.001 to 1000 parts by mass of an organic solvent (D) per 100 parts by mass of the cationically polymerizable compound (A). Furthermore, the organic solvent (D) can be an organic solvent (d1) that can dissolve the cationic polymerization initiator (B) by the same mass at 25 °C, and the thermally cationically polymerizable composition in each of the configurations can comprise 10 to 1000 parts by mass of the organic solvent (d1) per 100 parts by mass of the cationic polymerization initiator (B).

[0012] The thermally cationically polymerizable composition in each of the configurations can have an organic solvent (D) content of less than 10 parts by mass per 100 parts by mass of the cationic polymerization initiator (B). Furthermore, the thermally cationically polymerizable composition in each of the configurations can essentially contain no organic solvent (D).

[0013] The foregoing problems can also be solved by providing a cationic polymerization process in which the thermally cationically polymerizable composition in each of the configurations is optionally dried and then heated to promote cationic polymerization. Alternatively, the foregoing problems can be solved by providing a cationic polymerization process in which the thermally cationically polymerizable composition in each of the configurations is transported in the outdoor environment, optionally dried, and then heated to promote cationic polymerization. An adhesive or coating agent comprising the thermally cationically polymerizable composition is a preferred embodiment.

[0014] Furthermore, the above problems can be solved by providing a stabilizer (C) for a thermally cationically polymerizable composition, wherein the stabilizer (C) is represented by the following formula (2).

[0015] In formula (2) R 4 , R 5 and R 6 each independently an alkyl group with 1 to 10 carbon atoms, optionally having a substituent, an aryl group with 6 to 15 carbon atoms, optionally having a substituent, or an aralkyl group with 7 to 15 carbon atoms, optionally having a substituent. Advantageous effects of the invention

[0016] The thermally cationically polymerizable composition of the present invention exhibits a long pot life despite the use of a cationic polymerization initiator with a low polymerization initiation temperature. Accordingly, the thermally cationically polymerizable composition allows for a high degree of freedom in processes for its manufacture, storage, and transport, and the composition is subject to less variation in its physical properties during application and curing processes. Such a thermally cationically polymerizable composition is produced by the manufacturing process of the present invention. Furthermore, a thermally cationically polymerizable composition with a long pot life is successfully obtained through the use of the stabilizer of the present invention. Brief description of the drawing [ Fig. 1] Fig.1 is a series of DSC curves for thermally cationically polymerizable compositions in Example 1, Example 5, Comparative Example 1 and Comparative Example 6. Description of embodiments

[0017] The present invention relates to a thermally cationically polymerizable composition comprising a cationically polymerizable compound (A), a cationic polymerization initiator (B), and a stabilizer (C). That is, a composition comprising a cationically polymerizable compound (A), a cationic polymerization initiator (B), and a stabilizer (C) is used for thermal cationic polymerization. The thermally cationically polymerizable composition of the present invention undergoes pyrolysis of the cationic polymerization initiator (B) by heating, and a cationic species resulting from the pyrolysis reacts with the cationically polymerizable compound (A), initiating the polymerization reaction of the cationically polymerizable compound (A) and yielding a polymer. The stabilizer (C) acts to prevent the polymerization reaction from progressing during storage.The components are described in detail below.

[0018] The cationically polymerizable compound (A) can be, without limitation, any compound capable of undergoing cationic polymerization. Examples include: a compound with a cyclic ether group, such as an epoxy group and an oxetane group; a compound with a cyclic thioether group; a compound with a vinyl ether group; and a compound with a styryl group. Of these, the compound with a cyclic ether group, such as an epoxy group and an oxetane group, is preferred with respect to adhesion and chemical resistance. In particular, an epoxy compound having an epoxy group in the molecule is especially preferred. With respect to handling, it is preferred that the cationically polymerizable compound (A) be liquid at room temperature (25 °C). It is also preferred that the molecular weight of the cationically polymerizable compound (A) be between 100 and 700.

[0019] The epoxy compound can be a mono-epoxide, comprising one epoxy group in a molecule, or a poly-epoxide, comprising two or more epoxy groups in a molecule, and a mixture thereof can be used. To impart greater hardness and a higher modulus of elasticity to an epoxy resin through curing, it is preferred that the epoxy compound be a poly-epoxide. Typically, two to seven epoxy groups are contained in one molecule of a poly-epoxide compound. With regard to fluidity and the reduction of unreacted epoxy groups, it is preferred that two epoxy groups are contained in one molecule of the epoxy compound. For cationic polymerizability, an alicyclic epoxy compound is preferred, and a compound with an epoxycyclohexane group is particularly preferred.Accordingly, a compound with two epoxycyclohexane groups in one molecule is particularly preferred, and a representative example of this is 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.

[0020] The cationic polymerization initiator (B) is a compound represented by formula (1) shown below. The cationic polymerization initiator (B) decomposes upon heating and any exposure to R 1 , R 2 and R 3 It becomes a cation, and the remaining unit forms a sulfide. The cation thus produced from R 1 , R 2 or R 3 reacts with the cationically polymerizable compound (A), for example at an epoxy group, and the cationic polymerization proceeds from there.

[0021] In formula (1) R 1 , R 2 and R 3Each independently comprises an alkyl group with 1 to 10 carbon atoms, optionally containing a substituent, an aryl group with 6 to 15 carbon atoms, optionally containing a substituent, or an aralkyl group with 7 to 15 carbon atoms, optionally containing a substituent. R 1 , R 2 and R 3The groups can be identical or different. The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 4. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. The number of carbon atoms in the aryl group is preferably 6 to 10, and more preferably 6 to 8. Specific examples of the aryl group include a 4-hydroxyphenyl group and a 4-acetoxyphenyl group. The number of carbon atoms in the aralkyl group is preferably 7 to 11, and more preferably 7 to 9. Specific examples of the aralkyl group include a benzyl group, a 2-methylbenzyl group, a 4-methylbenzyl group, and a 1-naphthylmethyl group.

[0022] It is preferred that in formula (1) R 1 an aryl group or an alkyl group, R 2 an alkyl group or an aralkyl group and R 3 is an alkyl group.

[0023] In formula (1) XB(Rf 1 )4, Sb(R f 2 )6, P(R f 3 )6, N(R f 4 )2, C(R f 5 )3, Al(R f 6 )4 or Ga(R f 7 )4, where R f 1 to R f 7 Each independently consists of a fluorine-containing group selected from the group consisting of one fluorine atom, a perfluoroalkyl group with 1 to 6 carbon atoms, a perfluoroaryl group with 6 to 10 carbon atoms, a perfluoroalkyl-substituted aryl group with 7 to 14 carbon atoms, a perfluoroalkylsulfonyl group with 1 to 6 carbon atoms, and a perfluoroalkoxy group with 1 to 6 carbon atoms. B, Sb, P, N, C, Al, or Ga is selected as the central metal to which R is attached. f-Groups, each of which is a strong electron-withdrawing group containing fluorine, are bonded in such a way that as a whole they form a monovalent anionic species (X - ) form. Several R f -Groups bound to the same central element can be the same or different, however, each binding group must have an R f -group. Several perfluoroalkyl groups, perfluoroalkylsulfonyl groups, or perfluoroalkoxy groups bonded to a central element can be linked to one another by forming a perfluoroalkylene group, thus creating a ring. In each of these cases, the conjugate acid (HX) of the anionic species is a stronger acid than trifluoromethanesulfonic acid. Accordingly, in each of these cases, the pKa value of the conjugate acid (HX) of the anionic species at 25 °C is lower than that of trifluoromethanesulfonic acid.

[0024] Furthermore, it is preferred that in formula (1) R f1 a fluorine atom, a perfluoroaryl group with 6 to 10 carbon atoms, a perfluoroalkyl-substituted aryl group with 7 to 14 carbon atoms, or a perfluoroalkoxy group with 1 to 6 carbon atoms; R f 2 a fluorine atom; R f 3 a fluorine atom or a perfluoroalkyl group with 1 to 6 carbon atoms; R f 4 a perfluoroalkylsulfonyl group with 1 to 6 carbon atoms; R f 5 a perfluoroalkylsulfonyl group with 1 to 6 carbon atoms; R f 6 a perfluoroalkoxy group with 1 to 6 carbon atoms; and R f 7a fluorine atom, a perfluoroalkyl group with 1 to 6 carbon atoms, a perfluoroaryl group with 6 to 10 carbon atoms, or a perfluoroalkyl-substituted aryl group with 7 to 14 carbon atoms. In this case, too, several perfluoroalkyl groups, perfluoroalkylsulfonyl groups, or perfluoroalkoxy groups bonded to a central element can be linked together to form a ring by creating a perfluoroalkylene group.

[0025] In formula (1), the number of carbon atoms of the perfluoroalkyl group is preferably 1 to 4 and more preferably 1 to 3. Specific examples of the perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, a heptafluoroisopropyl group, and a nonafluoro-t-butyl group. The number of carbon atoms of the perfluoroaryl group is preferably 6 to 8 and more preferably 6 or 7. Specific examples of the perfluoroaryl group include a pentafluorophenyl group. The perfluoroalkyl-substituted aryl group is a group obtained by replacing at least some of the hydrogen atoms bonded to the aromatic ring of an aryl group with perfluoroalkyl groups, and any hydrogen atom bonded to the aromatic ring may remain unsubstituted. The number of carbon atoms of the perfluoroalkyl-substituted aryl group is preferably 7 to 12 and more preferably 7 to 10.Specific examples of the perfluoroalkyl-substituted aryl group include a 3,5-bistrifluoromethylphenyl group. The number of carbon atoms in the perfluoroalkylsulfonyl group is preferably 1 to 4, and more preferably 1 to 3. Specific examples of the perfluoroalkylsulfonyl group include a trifluoromethanesulfonyl group. A group obtained by bonding two perfluoroalkylsulfonyl groups such that the two sulfonyl groups are linked via a hexafluoropropylene group is also preferred. The number of carbon atoms in the perfluoroalkoxy group is preferably 1 to 4. Specific examples of the perfluoroalkoxy group include a nonafluoro-t-butyloxy group.

[0026] Preferred specific examples of the anion referred to in formula (1) as “X -The anions represented by formulas (1x) to (11x) below are included. Of these, anions that enable the cationic polymerization initiator (B) to readily generate a cation and that result in a low polymerization initiation temperature are of great importance with respect to the use of the thermally cationically polymerizable composition of the present invention. In this respect, the anions represented by formulas (1x) to (10x) are preferred, the anions represented by formulas (1x) to (7x) are more preferred, and the anions represented by formulas (1x) and (2x) are even more preferred.

[0027] Various sulfonium salts, which are commercially available as cationic polymerization initiators, can be used as the cationic polymerization initiator (B) for the compound represented by formula (1). Alternatively, the compound represented by formula (1) can be prepared by replacing one anion of a commercially available sulfonium salt as the starting material.

[0028] The stabilizer (C) is a compound represented by the following formula (2).

[0029] The anionic species in formula (2) is trifluoromethanesulfonate. The configuration of stabilizer (C), where the anionic species is trifluoromethanesulfonate, effectively inhibits the increase in viscosity of the thermally cationically polymerizable composition at low temperatures, thereby allowing the thermally cationically polymerizable composition to maintain the form of a low-viscosity liquid and consequently exhibiting a longer pot life. As also described in patent document 2, the compound represented by formula (2), which itself can act as a cationic polymerization initiator, prevents the thermally cationically polymerizable composition from becoming viscous during low-temperature storage for an extended period when combined with the more active cationic polymerization initiator (B).

[0030] In formula (2) R4 , R 5 and R 6 Each independently comprises an alkyl group with 1 to 10 carbon atoms, optionally containing a substituent, an aryl group with 6 to 15 carbon atoms, optionally containing a substituent, or an aralkyl group with 7 to 15 carbon atoms, optionally containing a substituent. R 4 , R 5 and R 6The groups can be identical or different. The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 4. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. The number of carbon atoms in the aryl group is preferably 6 to 10, and more preferably 6 to 8. Specific examples of the aryl group include a 4-hydroxyphenyl group and a 4-acetoxyphenyl group. The number of carbon atoms in the aralkyl group is preferably 7 to 11, and more preferably 7 to 9. Specific examples of the aralkyl group include a benzyl group, a 2-methylbenzyl group, a 4-methylbenzyl group, and a 1-naphthylmethyl group.

[0031] It is preferred that in formula (2) R 4 an aryl group or an alkyl group, R 5 an alkyl group or an aralkyl group and R 6is an alkyl group.

[0032] The compound represented by formula (2), which is used as the stabilizer (C), can be prepared by any manufacturing process without restriction. As described in patent document 2, the compound represented by formula (2) can be prepared by reacting sulfonium chloride and sodium trifluoromethanesulfonate. Alternatively, the compound represented by formula (2) can be prepared by reacting sulfonium methyl sulfate and sodium trifluoromethanesulfonate. Furthermore, the compound represented by formula (2) can be prepared by reacting a sulfide and an alkyltrifluoromethanesulfonate.

[0033] The thermally cationically polymerizable composition of the present invention comprises 0.01 to 20 parts by mass of the cationic polymerization initiator (B) per 100 parts by mass of the cationically polymerizable compound (A) and comprises 0.1 to 50 parts by mass of the stabilizer (C) per 100 parts by mass of the cationic polymerization initiator (B).

[0034] If the content of the cationic polymerization initiator (B) per 100 parts by mass of the cationically polymerizable compound (A) is less than 0.01 parts by mass, the polymerization reaction may proceed insufficiently, resulting in a cured product with lower hardness or larger amounts of unreacted monomers. The content of the cationic polymerization initiator (B) is preferably 0.02 parts by mass or more, and more preferably 0.04 parts by mass or more. Conversely, if the content of the cationic polymerization initiator (B) per 100 parts by mass of the cationically polymerizable compound (A) is more than 20 parts by mass, larger amounts of volatile decomposition products are generated, resulting in higher production costs. The content of the cationic polymerization initiator (B) is preferably 5 parts by mass or less, and more preferably 2 parts by mass or less.

[0035] If the stabilizer (C) content per 100 parts by mass of the cationic polymerization initiator (B) is less than 0.1 parts by mass, the thermally cationically polymerizable composition exhibits a disadvantageous lower storage stability and consequently a shorter pot life. The stabilizer (C) content is preferably 0.2 parts by mass or more, and more preferably 0.4 parts by mass or more. Conversely, if the stabilizer (C) content per 100 parts by mass of the cationic polymerization initiator (B) is more than 50 parts by mass, a polymerization reaction may proceed insufficiently at a relatively low temperature, resulting in a cured product with lower hardness or larger amounts of unreacted monomers. The stabilizer (C) content is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less.

[0036] The thermally cationically polymerizable composition of the present invention may comprise an organic solvent (D) in addition to the cationically polymerizable compound (A), the cationic polymerization initiator (B), and the stabilizer (C), and may comprise 0.001 to 1000 parts by mass of an organic solvent (D) per 100 parts by mass of the cationically polymerizable compound (A). The inclusion of an organic solvent may result in a lower viscosity, leading to improved coating properties. Furthermore, the cationic polymerization initiator (B) and the stabilizer (C) may readily dissolve in the thermally cationically polymerizable composition. When used for viscosity adjustment, the content of the organic solvent (D) may be 5 to 500 parts by mass or 10 to 200 parts by mass per 100 parts by mass of the cationically polymerizable compound (A).

[0037] In a preferred embodiment, the organic solvent (D) is an organic solvent (d1) that can dissolve the cationic polymerization initiator (B) by the same mass at 25 °C, and 10 to 1000 parts by mass of the organic solvent (d1) are contained per 100 parts by mass of the cationic polymerization initiator (B). This means that a small amount of a good solvent is required to dissolve the cationic polymerization initiator (B). Due to the low content of the organic solvent (d1), the thermally cationically polymerizable composition requires less energy in the drying process and is less likely to pollute the environment. The low content allows cationic polymerization to proceed without the drying process.The content of the organic solvent (d1) per 100 parts by mass of the cationic polymerization initiator (B) can be 20 to 500 parts by mass or 50 to 200 parts by mass.

[0038] In the preparation of the thermally cationically polymerizable composition comprising the organic solvent (d1) as described, the cationic polymerization initiator (B) and the stabilizer (C) are preferably dissolved beforehand in the organic solvent (d1) and then mixed with the cationically polymerizable compound (A). This process enables the homogeneous incorporation of the cationic polymerization initiator (B) and the stabilizer (C) into the thermally cationically polymerizable composition. Alternatively, the cationic polymerization initiator (B) can be dissolved beforehand in the organic solvent (d1) and then mixed with the cationically polymerizable compound (A) in which the stabilizer (C) has been dissolved.In the present invention, the stabilizer (C) exhibits better solubility in the cationically polymerizable compound (A) than the compound described in patent document 1 (sulfonium methyl sulfate: comparative example 1).

[0039] On the other hand, the organic solvent (D) content of the thermally cationically polymerizable composition can be less than 10 parts by mass per 100 parts by mass of the cationic polymerization initiator (B). This structure inhibits the formation of organic volatile components, and the drying process can be omitted. Furthermore, the thermally cationically polymerizable composition preferably comprises essentially no organic solvent (D); this structure also inhibits the formation of organic volatile components, and the drying process is no longer necessary. This is particularly important in manufacturing processes for electronic components and semiconductors, which are sensitive to contamination in working environments.

[0040] In the case where the thermally cationically polymerizable composition essentially does not comprise an organic solvent (D), as described above, the stabilizer (C) is preferably dissolved beforehand in the cationically polymerizable compound (A) and then mixed with the cationic polymerization initiator (B) to produce the thermally cationically polymerizable composition. Alternatively, both the cationic polymerization initiator (B) and the stabilizer (C) can be added to and mixed with the cationically polymerizable compound (A) to produce the thermally cationically polymerizable composition. In these cases, the cationic polymerization initiator (B) is preferably a cationic polymerization initiator with excellent solubility in organic compounds and a compound of formula (1), wherein XB(R) f 1)4 is preferred.

[0041] The thermally cationically polymerizable composition of the present invention may contain an additional component, different from the cationically polymerizable compound (A), the cationic polymerization initiator (B), the stabilizer (C), and the organic solvent (D), in such a way that the effects of the present invention are not inhibited. Various components, including fillers, reinforcing fibers, conductive particles, colorants, photopolymerization initiators, ultraviolet absorbers, photosensitizers, antioxidants, flame retardants, leveling agents, silane coupling agents, radically polymerizable compounds, (meth)acrylic resins, polyurethane resins, polyamide resins, and polyester resins, may be added as appropriate for the application.The mixing ratios of components added as solids without dissolving or melting and not directly involved in the cationic polymerization reaction, such as fillers, fibers, and particles, are not limited and are adjusted to suit the application. Such a mixing ratio can, for example, range from 0.1 to 1000 parts by mass per 100 parts by mass of the cationically polymerizable compound (A). The content of the additional component, which is homogeneously mixed with (A), (B), (C), and (D), is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0042] The preferred cationic polymerization process of the present invention is a process in which the thermally cationically polymerizable composition is optionally dried and then heated to promote cationic polymerization. In most cases, the thermally cationically polymerizable composition, which is in liquid form at room temperature, is heated to promote cationic polymerization (curing reaction), yielding a product (cured composition). The thermally cationically polymerizable composition is preferably dried at a temperature of 50 °C or less and then heated at 60 to 260 °C for 1 to 300 minutes to promote cationic polymerization.A heating temperature of 60 °C or higher allows the cationic polymerization initiator (B) to release a reactive cation, thus facilitating the progression of cationic polymerization. The heating temperature is more preferably 80 °C or higher, and even more preferably 100 °C or higher. Reacting at a higher temperature leads to a higher reaction rate and consequently allows the cationic polymerization to proceed in a shorter time. On the other hand, curing at a high temperature leads to shrinkage upon cooling after curing, which can occasionally cause problems with strong adhesion, and the high temperature can affect the electrical performance in applications of bonding and encapsulating electronic components, semiconductors, or the like.Therefore, the heating temperature is preferably 260 °C or less, more preferably 230 °C or less, and even more preferably 200 °C or less.

[0043] Due to the inclusion of the stabilizer (C), the thermally cationically polymerizable composition of the present invention retains its liquid form without an increase in viscosity for an extended period, thus exhibiting a long pot life. This allows for a longer storage period. This point has been demonstrated in examples in the present application, and it has been shown that an extension of approximately 3 days in the number of days elapsed (pot life) is achieved before the viscosity reaches twice that of the initial storage under refrigeration at 5 °C, in particular a pot life of 7 to 8 days, in contrast to 4 to 5 days with conventional stabilizers. The extension of the storage period under refrigeration by approximately 3 days is of great significance for process handling.In particular, whereas in most conventional cases the short pot life has necessitated the production of a thermally cationically polymerizable composition by mixing a cationically polymerizable compound (A), a cationic polymerization initiator (B) and a stabilizer (C) in the user's plant to carry out a heating process for curing, it becomes possible to mix a cationically polymerizable compound (A), a cationic polymerization initiator (B) and a stabilizer (C) to produce a thermally cationically polymerizable composition at a chemical manufacturer, then transport the thermally cationically polymerizable composition outdoors, subsequently dry it if necessary and then heat it to promote cationic polymerization.This can reduce the effort required by users to operate and handle mixing equipment and allows for batch production at a chemical manufacturer. Any means of transport can be used without restriction for outdoor transport; however, refrigerated transport with temperature control is preferred. The refrigeration temperature is preferably 15 °C or less, and more preferably 10 °C or less. To prevent freezing, however, the refrigeration temperature is preferably 0 °C or more.

[0044] Furthermore, it has been shown that the thermally cationically polymerizable composition of the present invention not only has a longer pot life, but also a lower polymerization initiation temperature than conventional stabilizers, as shown in DSC curves ( Fig.1) is shown in examples. Consequently, it was found that an increase in the polymerization initiation temperature can be inhibited, while an unnecessary polymerization reaction at the storage temperature is inhibited, thus enabling long-term storage and low-temperature curing combined. The temperature at which the exothermic onset of the thermally cationically polymerizable composition of the present invention is measured at a temperature increase (10 °C / min) using DSC is preferably 80 °C or less. The temperature at which the exothermic onset is more preferably 78 °C or less, and even more preferably 76 °C or less. Normally, the temperature at which the exothermic onset is 60 °C or more.

[0045] As it is in DSC curves ( Fig.1) As shown in the examples, the temperature at which the exothermic reaction begins is higher in a case without the use of the organic solvent (d1) (Example 5) than in a case where the organic solvent (d1) is used (Example 1). However, the rate of heat generation at an initial exothermic peak (first peak) is considerably higher, which is expected to be beneficial for rapid curing. Furthermore, the drying process is not required since no organic solvent is present, and the volatilization of the organic solvent (d1) in working environments can be avoided; these points are advantageous.

[0046] While the addition of a stabilizer to a thermally cationically polymerizable composition generally results in a cured product with a lower specific electrical resistance, the thermally cationically polymerizable composition of the present invention is less likely to exhibit a reduced specific electrical resistance when cured than when a conventional stabilizer is used. Accordingly, the thermally cationically polymerizable composition of the present invention is suitable for applications requiring a high level of electrical insulation. The specific electrical resistance of a cured product of the thermally cationically polymerizable composition of the present invention is preferably 3 × 10⁻⁶. 7 Ω · m or more and more preferably 4 × 10 7Ω·m or more. The specific electrical resistance for a case without the use of the organic solvent (d1) (Example 5) is lower than that for a case using an organic solvent and a conventional stabilizer. Although this is not important for common electrical insulation, making a different selection for different applications is preferred.

[0047] The described thermally cationically polymerizable composition is not limited to any particular application and is preferably used as a heat-curing liquid resin composition. The thermally cationically polymerizable composition of the present invention is curable at a relatively low temperature and exhibits good adhesion to resin, metal, etc., making it a preferred adhesive or coating agent. Any adhesive capable of bonding multiple elements is acceptable, and such adhesives include various types. For example, a composition containing conductive particles can be used as a conductive paste or anisotropic conductive film (ACF). Any coating capable of covering the surface of an element is acceptable, and such coating agents include various types.For example, the thermally cationically polymerizable composition of the present invention can even be used as a sealing or encapsulating material, as an insulating material, or as a photoresist. In addition to these applications, the thermally cationically polymerizable composition of the present invention is suitable for fiber-reinforced plastics (FRP) and nano-embossing materials. Because it can be cured at a relatively low temperature, the thermally cationically polymerizable composition of the present invention advantageously causes less thermal damage to electrical components, semiconductors, and the like. Furthermore, a reduction in the amount of volatile organic solvents is achieved, and in this respect as well, the thermally cationically polymerizable composition of the present invention is suitable for applications involving electronic components, semiconductors, and the like.

[0048] As explained so far, it has been shown that the thermally cationically polymerizable composition of the present invention, which contains the new stabilizer (C), exhibits a longer pot life than conventional stabilizers and can avoid an elevated temperature at which the exothermic reaction begins. The use of the compound represented by formula (2) as a stabilizer for a thermally cationically polymerizable composition is itself a novel approach. Accordingly, the problems of the present invention are also solved by providing the stabilizer (C) represented by formula (2) for a thermally cationically polymerizable composition. Consequently, the present invention provides a new and useful stabilizer. Examples Example 1 [Synthesis of a stabilizer]

[0049] In a 200 mL four-necked flask, 6.66 g (25 mmol) of 4-hydroxyphenyldimethylsulfonium methyl sulfate (“SAN-AID SI-S”, manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.: formula (2e) in Comparative Example 1), 4.3 g (25 mmol) of sodium trifluoromethanesulfonate, and 85 mL of ethanol were placed and stirred at 25 °C for 24 hours. The reaction solution was filtered, the resulting filtrate was concentrated, and then 100 mL of hexane was added to the concentrate and the resulting mixture was stirred. A precipitate formed was filtered off, and 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate (formula (2a) shown below) was obtained as white crystals in a yield of 95%. 1 H-NMR (400 MHz, CD3CN): δ8.50 (s, 1H), 7.82 (d, 2H), 7.11 (d, 2H), 3.17 (s, 6H)]. Details of the stabilizer (2a) are summarized in Table 1. [Solubility of the stabilizer]

[0050] At 25 °C, the process of adding 1 g of the stabilizer (2a) to a 30 mL screw-top tube, adding a 1 g portion of solvent, and subsequently mixing with an ARE-310 planetary centrifugal mixer manufactured by THINKY CORPORATION was repeated, and the mass of solvent required to completely dissolve the stabilizer (2a), Ws (g), was determined. The solubility (S), i.e., the mass of the substance to be dissolved that is soluble in 100 g of solvent, was determined using the expression shown below. The solubility for successful dissolution with 1 g of solvent was reported as ≥100, and the solubility for incomplete dissolution even with the addition of 100 g of solvent was reported as <1. Water, propylene carbonate (PC), methyl isobutyl ketone (MIBK) and propylene glycol monomethyl ether acetate (PGMAc) were used as solvents.“CELLOXIDE 2021P”, which is 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, a cationically polymerizable compound, was subjected to the same test to evaluate the solubility of the stabilizer. The results showed that the solubility of the stabilizer (2a) was 100 [g / 100 g solvent] or more for water, PC, MIBK, and PGMAc, and 25 [g / 100 g solvent] for “CELLOXIDE 2021P”. S[g / 100 g solvent]=1 / (Ws / 100) [Production of a thermally cationically polymerizable composition]

[0051] A thermally cationically polymerizable composition was prepared using the stabilizer (2a) thus obtained. First, 20.0 mg of 4-acetoxyphenylbenzylmethylsulfoniumtetrakis(pentafluorophenyl)borate (“SAN-AID SI-B3A”, manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.: formula (1a) shown below) as a polymerization initiator and 0.2 mg of the stabilizer (2a) were placed in a 10 mL screw-top tube and completely dissolved by adding 20.0 mg of propylene carbonate as a solvent, thus preparing an initiator solution.20.1 mg of the prepared initiator solution were placed into a 30 mL screw-cap tube, 10 g of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ("CELLOXIDE 2021P", manufactured by Daicel Corporation: formula (3a) shown below) as a cationically polymerizable compound were added, and the resulting mixture was immediately mixed using the ARE-310 planetary centrifugal mixer to produce a thermally cationically polymerizable composition. Details of the obtained thermally cationically polymerizable composition are summarized in Table 2. [Storage stability]

[0052] The prepared thermally cationically polymerizable composition was placed in a 30 mL screw-top tube, which was stored in a thermostatically controlled chamber at 5 °C. The viscosity of the sample was measured at 25 °C each day. The E-type viscometer "TV-100EH" manufactured by Toki Sangyo Co., Ltd. was used for viscosity measurement. The pot life was determined to be the number of days it took for the viscosity to double its initial viscosity (7 days). [Heat hardening property]

[0053] A 5.0 mg portion was weighed out from the prepared thermally cationically polymerizable composition (heat-curing composition) and the temperature was increased from 30 °C to 310 °C at a rate of 10 °C / min in a nitrogen gas stream of 40 mL / min using the X-DSC7000 differential scanning calorimeter, manufactured by Hitachi High-Tech Corporation, so that a DSC curve was obtained. Fig.Figure 1 shows the obtained DSC curve. The heat generation in the DSC curve was investigated in the range of approximately 70 to approximately 250 °C, and three exothermic peaks were found. Of these, the initial exothermic peak (most prevalent on the low-temperature side) was defined as the first exothermic peak. The temperature of the first exothermic peak was 81 °C, and the heat generation rate (peak height) at the first exothermic peak was 8 mW. The temperature of exothermic onset, which is the temperature at the intersection of the tangent line at the inflection point on the low-temperature side of the first exothermic peak and the baseline, was 72 °C. [Specific electrical resistance]

[0054] A comb-shaped, tinned copper electrode was formed on a polyimide resin film. A sample was prepared by applying the thermally cationically polymerizable composition to an electrode surface of the tinned copper electrode and placed on the LT-451 dielectric analyzer, manufactured by SysCom Corp. The resistivity was monitored while an AC voltage of 1 V at a frequency of 1 kHz was applied and the sample temperature was maintained at 70 °C. The thermally cationically polymerizable composition was cured after 2 hours, and the cured product exhibited a resistivity of 5.1 × 10⁻⁶ Ω·m. 7 Ω· m. The thermally cationically polymerizable composition, after curing, was firmly bonded to both the metal surface of the comb-shaped electrode and the resin surface of its substrate. Example 2

[0055] In a 200 mL four-necked flask, 3.51 g (25 mmol) of 4-(methylthio)phenol, 3.85 g (25 mmol) of diethyl sulfate, and 25 mL of acetonitrile were placed and stirred at 40 °C for 24 hours. The resulting reaction solution was concentrated, yielding 4-hydroxyphenylmethylethylsulfonium ethyl sulfate as an intermediate. To this intermediate, 4.3 g (25 mmol) of sodium trifluoromethanesulfonate and 85 mL of ethanol were added, and the resulting mixture was stirred at 25 °C for 24 hours. The reaction solution was filtered, the resulting filtrate was concentrated, and then 100 mL of hexane was added to the concentrate, and the resulting mixture was stirred. A generated precipitate was filtered off, yielding 4-hydroxyphenylmethylethylsulfonium trifluoromethanesulfonate (formula (2b) shown below) as a clear liquid in a yield of 84%.With the obtained stabilizer (2b), a thermally cationically polymerizable composition was prepared in the same way as in Example 1 [. 1 H-NMR (400 MHz, CD3CN): δ9.62 (s, 1H), 7.73 (d, 2H), 7.10 (d, 2H), 3.96 (q, 2H), 3.13 (s, 3H), 1.16 (t, 3H)]. The stabilizer (2b) and the obtained thermally cationically polymerizable composition were evaluated in the same manner as in Example 1; the results are shown in Table 1 and Table 2. Example 3

[0056] In a 200 mL four-necked flask, 3.51 g (25 mmol) of 4-(methylthio)phenol, 3.16 g (25 mmol) of benzyl chloride, and 25 mL of acetonitrile were placed and stirred at 40 °C for 24 hours. The resulting reaction solution was concentrated, yielding 4-hydroxyphenylmethylbenzylsulfonium chloride as an intermediate. The same procedures as in Example 2 were carried out, except that the intermediate was used, giving 4-hydroxyphenylmethylbenzylsulfonium trifluoromethanesulfonate (formula (2c) shown below) as white crystals in a yield of 96%. 1¹H NMR (400 MHz, CD3CN): δ6.72 to 7.40 (m, ¹⁰H), 4.43 (q, ²H), 2.79 (s, ³H). A thermally cationically polymerizable composition was prepared using the obtained stabilizer (2c) in the same manner as in Example 1. The stabilizer (2c) and the obtained thermally cationically polymerizable composition were evaluated in the same manner as in Example 1; the results are shown in Table 1 and Table 2. Example 4

[0057] In a 200 mL four-necked flask, 3.46 g (25 mmol) of benzyl methyl sulfide, 3.15 g (25 mmol) of dimethyl sulfate, and 25 mL of acetonitrile were placed and stirred at 40 °C for 24 hours. The resulting reaction solution was concentrated, yielding benzyldimethylsulfonium methyl sulfate as an intermediate. The same procedures as in Example 2 were carried out, except that the intermediate was used, yielding benzyldimethylsulfonium trifluoromethanesulfonate (formula (2d) shown below) as a clear liquid in a yield of 93%. 1¹H NMR (400 MHz, CD3CN): δ7.15 to 7.50 (m, 5H), 4.00 (s, 2H), 2.80 (s, 6H). A thermally cationically polymerizable composition was prepared using the obtained stabilizer (2d) in the same manner as in Example 1. The stabilizer (2d) and the obtained thermally cationically polymerizable composition were evaluated in the same manner as in Example 1; the results are shown in Table 1 and Table 2. Example 5

[0058] In a 30 mL screw-cap tube, 0.2 g of the stabilizer (2a) obtained in Example 1 was placed, and 20 g of the cationically polymerizable compound "CELLOXIDE 2021P" were added and completely dissolved by mixing using the "ARE-310" planetary centrifugal mixer. Subsequently, 20.0 mg of "SAN-AID SI-B3A" (1a) was added as a polymerization initiator, and the resulting mixture was further mixed using a planetary centrifugal mixer; consequently, a thermally cationically polymerizable composition free of the solvent propylene carbonate was prepared. The obtained thermally cationically polymerizable composition was evaluated in the same manner as in Example 1; the results are shown in Table 1, Table 2, and the Fig. 1 shown. Comparative example 1

[0059] A thermally cationically polymerizable composition was prepared in the same manner as in Example 1, except that 0.2 mg of 4-hydroxyphenyldimethylsulfonium methyl sulfate (“SAN-AID SI-S”, manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.: formula (2e) shown below) was used as a stabilizer. The stabilizer (2e) and the thermally cationically polymerizable composition were evaluated in the same manner as in Example 1; the results are shown in Table 1, Table 2, and the Fig. 1 shown. As in Example 5, the preparation of a thermally cationically polymerizable composition was attempted without the use of the solvent (PC), whereas compound (2e) did not dissolve completely. Comparative example 2

[0060] Into a 200 mL four-necked flask, 6.66 g (25 mmol) of 4-hydroxyphenyldimethylsulfonium methyl sulfate (“SAN-AID SI-S”, manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.: formula (2e) below in comparative example 1), 2.95 g (25 mmol) of sodium methyl sulfite, and 85 mL of ethanol were added and stirred at 25 °C for 24 hours. The reaction solution was filtered, and the resulting filtrate was concentrated. Then, 100 mL of hexane was added to the concentrate, and the resulting mixture was stirred. A precipitate formed was filtered off, and 4-hydroxyphenyldimethylsulfonium methyl sulfite (formula (2f) shown below) was obtained in 91% yield. 1H-NMR (400 MHz, CD3OD): δ7.87 (d, 2H), 7.12 (d, 2H), 5.18 (s, 1H), 3.26 (s, 6H), 2.71 (s, 3H). A thermally cationically polymerizable composition was prepared using the obtained stabilizer (2f) in the same manner as in Example 1. The stabilizer (2f) and the obtained thermally cationically polymerizable composition were evaluated in the same manner as in Example 1; the results are shown in Table 1 and Table 2. Comparative example 3

[0061] In the same manner as in Comparative Example 2, except that 2.95 g of sodium methyl sulfite, as specified in Comparative Example 2, were changed to 3.7 g of sodium dimethyl phosphate salt, 4-hydroxyphenyldimethylsulfonium dimethyl phosphate (formula shown below (2g)) was obtained in a yield of 85% [ 1¹H NMR (400 MHz, CD3OD): δ7.89 (d, 2H), 7.15 (d, 2H), 5.90 (s, 1H), 3.59 (d, 6H), 3.29 (s, 6H). A thermally cationically polymerizable composition was prepared using the obtained stabilizer (2g) in the same manner as in Example 1. The stabilizer (2g) and the obtained thermally cationically polymerizable composition were evaluated in the same manner as in Example 1; the results are shown in Table 1 and Table 2. Comparative example 4

[0062] In the same manner as in Comparative Example 2, except that 2.95 g of sodium methyl sulfite, as specified in Comparative Example 2, were changed to 4.86 g of sodium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium paratoluenesulfonate (formula (2h) shown below) was obtained in a yield of 89% [ 1¹H NMR (400 MHz, CD3CN): δ9.02 (s, 1H), 7.69 (d, 4H), 7.15 (d, 2H), 7.05 (d, 2H), 3.09 (s, 6H), 2.26 (s, 3H). A thermally cationically polymerizable composition was prepared using the obtained stabilizer (2h) in the same manner as in Example 1. The stabilizer (2h) and the obtained thermally cationically polymerizable composition were evaluated in the same manner as in Example 1; the results are shown in Table 1 and Table 2. Comparative example 5

[0063] In the same manner as in Comparative Example 2, except that the 2.95 g of sodium methyl sulfite given in Comparative Example 2 were changed to 2.95 g of sodium methanesulfonate, 4-hydroxyphenyldimethylsulfonium methanesulfonate (formula (2i) shown below) was obtained in a yield of 94% [ 1¹H NMR (400 MHz, CD3CN): δ7.75 (d, 2H), 7.15 (d, 2H), 3.28 (s, 1H), 3.09 (s, 6H), 2.76 (s, 3H). A thermally cationically polymerizable composition was prepared using the obtained stabilizer (2i) in the same manner as in Example 1. The stabilizer (2i) and the obtained thermally cationically polymerizable composition were evaluated in the same manner as in Example 1; the results are shown in Table 1 and Table 2. Comparative example 6

[0064] A thermally cationically polymerizable composition was prepared without the use of a stabilizer. First, an initiator solution was prepared by adding 20.0 mg of SAN-AID SI-B3A (formula (1a) in Example 1) as the polymerization initiator and 20.0 mg of propylene carbonate as the solvent to a 10 mL screw-top tube and dissolving completely. A thermally cationically polymerizable composition was prepared in the same manner as in Example 1, except that the initiator solution thus obtained was used. The resulting thermally cationically polymerizable composition was evaluated in the same manner as in Example 1; the results are shown in Table 1, Table 2, and the Fig. 1 shown. [Table 1] stabilizer solubility Structural formula cation Anion [g / 100 g solvent] R 1 R 2 R 3 x Water PC MIBK PGMAc 2021 P Example 1 (2a) 4-Hydroxyphenyl Me Me TfO ≥100 ≥100 ≥100 ≥100 25 Example 2 (2b) 4-Hydroxyphenyl Me Et TfO ≥100 ≥100 ≥100 2100 25 Example 3 (2c) 4-Hydroxyphenyl Bn Me TfO ≥100 ≥100 ≥100 ≥100 20 Example 4 (2d) Me Bn Me TfO ≥100 ≥100 ≥100 ≥100 25 Example 5 (2a) 4-Hydroxyphenyl Me Me TfO ≥100 ≥100 ≥100 ≥100 25 Comparative example 1 (2e) 4-Hydroxyphenyl Me Me MeSO4 ≥100 <1 <1 <1 <1 Comparative example 2 (2f) 4-Hydroxyphenyl Me Me MeSO3 ≥100 10 <1 <1 <1 Comparative example 3 (2g) 4-Hydroxyphenyl Me Me Me2PO4 ≥100 <1 <1 <1 <1 Comparative example 4 (2h) 4-Hydroxyphenyl Me Me TsO ≥100 ≥100 <1 <1 <1 Comparative example 5 (2i) 4-Hydroxyphenyl Me Me MsO ≥100 <1 <1 <1 <1 Comparative example 6 No - - - - - - - - - [Table 2] Polymerizable compound Polymerization initiator solvent stabilizer Potting time Temperature at the onset of exothermic activity First peak temperature First peak heat generation rate Specific electrical resistance (100 pieces) (0.1 parts) (0.1 parts) (0.001 pieces) (days) (°C) (°C) (mW) (Ω · m) Example 1 2021P SI-B3A PC (2a) 7 72 81 8 5,1 × 10 7 Example 2 2021P SI-B3A PC (2b) 7 71 82 8 5,3 × 10 7 Example 3 2021P SI-B3A PC (2c) a 72 80 8 5,2 × 10 7 Example 4 2021P SI-B3A PC (2d) 7 71 81 8 6,0 × 10 7 Example 5 2021P SI-B3A None (2a) 8 79 85 28 7,8 × 10 6 Comparative example 1 2021P SI-B3A PC (2e) 4 81 90 5 2,3 × 10 7 Comparative example 2 2021P SI-B3A PC (2f) 4 82 88 5 2,2 × 10 7 Comparative example 3 2021P SI-B3A PC (2g) 4 83 88 4 2,1 × 10 7 Comparative example 4 2021P SI-B3A PC (2h) 5 81 91 4 1,9 × 10 7 Comparative example 5 2021P SI-B3A PC (2i) 5 82 90 5 1,7 × 10 7 Comparative example 6 2021 P SI-B3A PC None 1 58 71 8 4,6 × 10 10 QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] JP 2019-189698 A

[0005] JP 2004-217551 A

[0005]

Claims

[1] Thermally cationically polymerizable composition comprising a cationically polymerizable compound (A), a cationic polymerization initiator (B) represented by formula (1) shown below, and a stabilizer (C) represented by formula (2) shown below, wherein the thermally cationically polymerizable composition comprises 0.01 to 20 parts by mass of the cationic polymerization initiator (B) per 100 parts by mass of the cationically polymerizable compound (A) and comprises 0.1 to 50 parts by mass of the stabilizer (C) per 100 parts by mass of the cationic polymerization initiator (B); where R 1 , R 2 and R 3each independently comprises an alkyl group with 1 to 10 carbon atoms, optionally having a substituent, an aryl group with 6 to 15 carbon atoms, optionally having a substituent, or an aralkyl group with 7 to 15 carbon atoms, optionally having a substituent; XB(Rf 1 )4, Sb(R f 2 )6, P(R f 3 )6, N(R f 4 )2, C(R f 5 )3, Al(R f 6 )4 or Ga(R f 7 )4 is, where R f 1 to R f 7each independently comprises a fluorine-containing group selected from the group consisting of a fluorine atom, a perfluoroalkyl group with 1 to 6 carbon atoms, a perfluoroaryl group with 6 to 10 carbon atoms, a perfluoroalkyl-substituted aryl group with 7 to 14 carbon atoms, a perfluoroalkylsulfonyl group with 1 to 6 carbon atoms, and a perfluoroalkoxy group with 1 to 6 carbon atoms; and several perfluoroalkyl groups, perfluoroalkylsulfonyl groups, or perfluoroalkoxy groups are optionally linked together to form a ring. where R 4 , R 5 and R 6 Each is independently an alkyl group with 1 to 10 carbon atoms, optionally having a substituent, an aryl group with 6 to 15 carbon atoms, optionally having a substituent, or an aralkyl group with 7 to 15 carbon atoms, optionally having a substituent. [2] Thermally cationically polymerizable composition according to claim 1, wherein, in formula (1), R f 1 a fluorine atom, a perfluoroaryl group with 6 to 10 carbon atoms, a perfluoroalkyl-substituted aryl group with 7 to 14 carbon atoms, or a perfluoroalkoxy group with 1 to 6 carbon atoms; R f 2 a fluorine atom; R f 3 a fluorine atom or a perfluoroalkyl group with 1 to 6 carbon atoms; R f 4 a perfluoroalkylsulfonyl group with 1 to 6 carbon atoms; R f 5 a perfluoroalkylsulfonyl group with 1 to 6 carbon atoms; R f 6 a perfluoroalkoxy group with 1 to 6 carbon atoms; and R f 7a fluorine atom, a perfluoroalkyl group with 1 to 6 carbon atoms, a perfluoroaryl group with 6 to 10 carbon atoms, or a perfluoroalkyl-substituted aryl group with 7 to 14 carbon atoms. [3] Thermally cationically polymerizable composition according to claim 1 or 2, comprising 0.001 to 1000 parts by mass of an organic solvent (D) per 100 parts by mass of the cationically polymerizable compound (A). [4] Thermally cationically polymerizable composition according to claim 3, wherein the organic solvent (D) is an organic solvent (d1) that can dissolve the cationic polymerization initiator (B) with the same mass at 25 °C, and the thermally cationically polymerizable composition comprises 10 to 1000 parts by mass of the organic solvent (d1) per 100 parts by mass of the cationic polymerization initiator (B). [5] Thermally cationically polymerizable composition according to claim 1 or 2, comprising an organic solvent (D) content of less than 10 parts by mass per 100 parts by mass of the cationic polymerization initiator (B). [6] Thermally cationically polymerizable composition according to claim 5, comprising essentially no organic solvent (D). [7] A cationic polymerization process in which the thermally cationically polymerizable composition according to any one of claims 1 to 6 is optionally dried and then heated to promote a cationic polymerization. [8] A cationic polymerization process in which the thermally cationically polymerizable composition according to any one of claims 1 to 6 is transported in the outdoor area, then optionally dried and then heated to promote a cationic polymerization. [9] Adhesive or coating agent comprising the thermally cationically polymerizable composition according to any one of claims 1 to 6. [10] Stabiliser (C) for a thermally cationically polymerizable composition, wherein the stabilizer (C) is represented by the following formula (2): where R 4 , R 5 and R 6 Each is independently an alkyl group with 1 to 10 carbon atoms, optionally having a substituent, an aryl group with 6 to 15 carbon atoms, optionally having a substituent, or an aralkyl group with 7 to 15 carbon atoms, optionally having a substituent.

Images