JP5815463B2 - Method for producing cationic curing catalyst - Google Patents

Description

The present invention relates to a method for producing a cationic curing catalyst. More specifically, the present invention relates to a cationic curing catalyst that contains a cationically curable compound and can be suitably used as a catalyst for a resin composition that is cured by a cationic curing reaction.

The cationic curing catalyst is a catalyst that contains a cationically curable compound, generates cationic species from the catalyst by heat, light, or the like, and accelerates the curing reaction of the composition that cures by the cationic curing reaction. Cationic curing (polymerization) has advantages such as no inhibition of curing by oxygen and small shrinkage during curing compared to radical polymerization, and resin compositions using cationic curing are expected to be applied in various fields. Yes. Specifically, for example, various applications such as electrical / electronic members, optical members, molding materials, paints, adhesive materials, etc. have been studied, and the properties required for each application are excellent. Development of a cationic curable resin composition is desired.

As a conventional cationic curable resin composition, for example, a curable resin composition containing a curable resin and a curing catalyst containing a Lewis acid containing trivalent boron and a nitrogen-containing molecule is disclosed. (For example, refer to Patent Document 1). Patent Document 1 describes that such a curable resin composition is cured using an acid anhydride, and describes that such a composition is used as an underfill material having lead-free solder. Yes.
Also disclosed are an onium salt comprising an onium cation and an imidazolide anion having a specific structure represented by formula (II), and a composition comprising the onium salt and a cationically polymerizable or crosslinkable resin. (For example, see Patent Document 2 and Non-Patent Document 1). Moreover, the silicone composition which can be superposed | polymerized and / or bridge | crosslinked by a cationic process using the Lewis adduct initiator activated by the heating of 50 to 100 degreeC is disclosed (for example, refer patent document 3).

Furthermore, for the polymerization and / or crosslinking of polyorganosiloxane type monomers, oligomers and / or polymers having an organic functional group comprising a boron derivative represented by a specific structural formula and a solvated form thereof. Disclosed are a heat-activated initiator and a polymerizable and / or cross-linkable composition comprising the polyorganosiloxane-type monomer, oligomer and / or polymer having the heat-activated initiator and an organic functional group. (For example, refer to Patent Document 4). Patent Document 4 describes the use of this composition as a coating material for dental restoration materials, electrical and electronic parts, and the like.
Furthermore, an epoxy resin (A), a curing agent (B), an onium salt (C) that does not contain a halogen ion in the counter anion, and a tri-substituted boron (D) in which no halogen is directly substituted for boron are essential components. The composition is disclosed (for example, refer patent document 5). Patent Document 5 describes that this composition is used as a semiconductor sealing material or a laminate.

Special table 2008-540407 International Publication No. 03/062208 International Publication No. 02/092665 Special table 2003-515617 JP-A-11-181060

4 people outside Kangtai Ren, “Macromolecules”, 2002, No. 35, p. 1632-1637

As described above, cation curable resin compositions that are applicable to various uses are being studied, and in any of these resin compositions, a cation curing catalyst is used. Applications for which application of the cationic curable resin composition is considered include applications in which the resin composition is molded and used such as optical materials (members) and machine part materials, and resin compositions such as adhesives. Some products are in the form of products, and are cured when used. In applications where the resin composition is used after being molded, the resin composition can be freely molded. Therefore, the resin composition may be in the form of a resin composition without curing until the resin composition is subjected to a curing step. In addition, in applications such as adhesives, it is required to be in the form of a resin composition until it is used. Thus, in order to make the cation curable resin composition suitable for various uses, not only can it be cured, but the form of the resin composition must be stably maintained until curing is required. Is required. The invention disclosed in the above document cannot be said to have been sufficiently studied to enhance the storage stability of a resin composition containing a cationic curing catalyst, and the cationic curing resin composition has excellent storage stability. There was room for a device to develop a cationic curing catalyst capable of

This invention is made | formed in view of the said present condition, and aims at providing the cation curing catalyst which makes it possible to improve the storage stability of a cation curable resin composition.

The present inventor has made various studies on a cationic curing catalyst capable of improving the storage stability of a cationic curable resin composition. As a result, Lewis has a structure in which one or more fluorinated aromatic rings are bonded to a boron atom. A cationic curing catalyst is prepared from an acid and a Lewis base, and at that time, a Lewis acid and a Lewis base are mixed to produce a cationic curing catalyst under the condition that the amount of water in the Lewis acid is not more than a predetermined amount. Then, the resin composition using the produced cationic curing catalyst was found to be excellent in storage stability capable of stably maintaining the form of the resin composition, and reached the present invention. is there.
This production method is a useful production method in that a cationic curing catalyst excellent in storage stability can be produced by a simple method of controlling the amount of water present when mixing a Lewis acid and a Lewis base.

That is, the present invention is a method for producing a cationic curing catalyst, which comprises the following general formula (1):

(In the formula, R is the same or different and represents a hydrocarbon group which may have a substituent. X is an integer of 1 to 5, and is the same or different and is a fluorine atom bonded to an aromatic ring. A is an integer of 1 or more, b is an integer of 0 or more, and a + b = 3 is satisfied.) The amount of water is less than 55 mol% with respect to the Lewis acid represented by And a method for producing a cationic curing catalyst, wherein the Lewis acid and a Lewis base are mixed.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

In the method for producing a cationic curing catalyst of the present invention, the Lewis acid and the Lewis base are mixed under the condition that the amount of water is less than 55 mol% with respect to the Lewis acid represented by the general formula (1). It is characterized by. A resin composition containing a cationic curing catalyst produced by such a production method has excellent storage stability. If mixing of Lewis acid and Lewis base is carried out under the condition that the amount of water is less than 55 mol% with respect to Lewis acid, even if water is added thereafter, the resin composition using the cation curing catalyst Is excellent in storage stability. About this reason, it estimates as follows.
When a cationic curing catalyst formed from a Lewis acid and a Lewis base represented by the general formula (1) acts as a catalyst, a cation is generated in the resin by binding the Lewis acid dissociated with the Lewis base to the resin. The curing reaction proceeds by the action of the cationic species. As described above, in order for the cationic curing catalyst formed from the Lewis acid represented by the general formula (1) and the Lewis base to exhibit catalytic activity, the Lewis acid needs to be dissociated from the Lewis base. It can be said that the base has an action of suppressing the expression of the catalytic activity of Lewis acid. On the other hand, water has an unshared electron pair and can be coordinated to a Lewis acid, but it is only a mixture of a Lewis acid represented by the general formula (1) and water. When blended with a resin, it has been confirmed that the resin hardens immediately because the catalytic activity is too high. From these, when water is present when a Lewis acid and a Lewis base are mixed to form a cationic curing catalyst, the coordination of the Lewis base to the Lewis acid is inhibited, and the coordination of the Lewis base to the Lewis acid is weakened. The Lewis base is easily dissociated from the Lewis acid, and as a result, such a cationic curing catalyst causes the resin to cure as the dissociation of the Lewis base from the Lewis acid progresses over time in the resin composition. Conceivable. On the other hand, by reducing the amount of water present when mixing the Lewis acid and the Lewis base to a predetermined amount or less, the proportion of the cationic curing catalyst in which the coordination of the Lewis base to the Lewis acid is inhibited is suppressed to a certain level or less. As a result, it is considered that a cationic curing catalyst in which the expression of the catalytic activity of Lewis acid is sufficiently suppressed can be obtained. Here, it is considered that one molecule of water can coordinate to two molecules of Lewis acid. When the amount of water exceeds 50 mol% with respect to the Lewis acid, the coordination of Lewis base by water is performed. It is thought that it greatly inhibits. If it is less than 55 mol%, it is considered that the influence of inhibition is not large, and it is considered that the use of such a cation curing catalyst makes the cation curable resin composition excellent in storage stability. Also, if the Lewis base is sufficiently coordinated to the Lewis acid, the addition of water will not significantly affect the coordination of the Lewis base to the Lewis acid. If the amount of water is less than 55 mol% with respect to the Lewis acid, the resin composition using the cation curing catalyst has excellent storage stability even when water is added thereafter. It will be a thing.
In this regard, when tris (pentafluorophenyl) borane (TPB) is used as the Lewis acid, when TPB is mixed with an amine which is a Lewis base under the condition that the amount of water is less than 55 mol% with respect to TPB, ¹⁹ F In -NMR measurement, it is confirmed that the position of the peak of the F atom of TPB is changed as compared with that before addition of the amine, and it is confirmed that structural change has occurred in TPB due to coordination of the amine. On the other hand, in the case of mixing with amine in the presence of 55 mol% or more of water with respect to TPB, the position of the peak of F atom of TPB does not change, and when amine is added in the presence of predetermined amount of water It is confirmed that no structural change occurs in TPB even when amine is added. This NMR measurement result can be said to support the fact that the coordination of Lewis base to Lewis acid is inhibited by the presence of water.

The method for producing a cationic curing catalyst of the present invention comprises a step of mixing the Lewis acid and a Lewis base under the condition that the amount of water is less than 55 mol% with respect to the Lewis acid represented by the general formula (1). As long as the amount of water is less than 55 mol% with respect to the Lewis acid represented by the general formula (1), at least a part of the Lewis base may include other steps. As long as it is mixed, it corresponds to the manufacturing method of the cationic curing catalyst of this invention.
Moreover, 1 type may be used for the Lewis acid represented by General formula (1), and a Lewis base, and 2 or more types may be used for it.

As described above, as long as at least a part of the Lewis base is mixed with the Lewis acid under the condition that the amount of water is less than 55 mol% with respect to the Lewis acid represented by the general formula (1), This corresponds to the method for producing a cationic curing catalyst of the invention, and all of the Lewis base is subjected to the Lewis acid under the condition that the amount of water is less than 55 mol% with respect to the Lewis acid represented by the general formula (1). It is preferable to be mixed with. For this purpose, after the step of adjusting the amount of water so that the amount of water is less than 55 mol%, the Lewis acid is adjusted to a Lewis acid adjusted to an amount of water of less than 55 mol%. It is preferable to perform a step of adding a base and mixing a Lewis acid and a Lewis base.

In the step of mixing the Lewis acid and the Lewis base under the condition that the amount of water is less than 55 mol% with respect to the Lewis acid represented by the general formula (1), the amount of water is However, the amount of water is preferably low from the viewpoint of further improving the storage stability. However, from the viewpoint of curability and heat resistance (heat-resistant colorability), it is preferably 30 mol% or more, and more preferably 40 mol% or more.
In addition, when the Lewis acid compound represented by the general formula (1) is synthesized, it may be obtained in a state containing water, and how much water is contained depends on the Lewis acid synthesis method. In the production method of the present invention, the amount of water under the condition that the molar ratio to the Lewis acid represented by the general formula (1) is less than 55 mol% is the water contained in the Lewis acid represented by the general formula (1). Means a condition that the molar ratio is less than 55 mol% with respect to the Lewis acid represented by the general formula (1).
That is, it means that the Lewis acid and the Lewis base are mixed under the condition that the amount of water is less than 55 mol% with respect to the pure content of the Lewis acid compound represented by the general formula (1).
The presence form of “water” in the stage of mixing the Lewis base is not limited. For example, the water molecule may be coordinated to a Lewis acid or may be independently present.

The step of mixing the Lewis acid and the Lewis base may be performed using a solvent. In the case of using a solvent, it is preferable to perform a step of adding a solvent to the Lewis acid and dissolving the Lewis acid in the solvent, and then adding a Lewis base thereto and mixing the Lewis acid and the Lewis base. By doing so, the mixing state of the Lewis acid and water can be made uniform, so that the mixing fluctuation during mixing of the Lewis acid and the Lewis base can be reduced in production.
The temperature and time of the step of dissolving the Lewis acid in the solvent can be appropriately set so that the Lewis acid is dissolved in the solvent.

The solvent is not particularly limited as long as it can dissolve a Lewis acid or a Lewis base, but an organic solvent is preferable from the viewpoint of affinity with a resin. Organic solvents include ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, γ-butyrolactone, etc.), ether solvents (diethyl ether, tetrahydrofuran, etc.), alcohol solvents (methanol, ethanol, propanol, butanol, etc.), aromatic One or more of group solvents (toluene, xylene, etc.), ester solvents (methyl acetate, ethyl acetate, etc.) and halogen solvents (chloroform, dichloromethane, etc.) are preferred. More preferred are ketone solvents, ether solvents, and aromatic solvents having no OH group or N group from the viewpoint of not affecting the reactivity.

The step of mixing the Lewis acid and the Lewis base is preferably performed at -20 to 100 ° C. More preferably, it is 5-60 degreeC.
Moreover, what is necessary is just to adjust suitably the time which performs the process of mixing with the quantity of the Lewis acid to be used or a Lewis base, but it is preferable to carry out for 3 to 600 minutes. More preferably, it is 30 to 120 minutes.
In addition, the step of mixing the Lewis acid and the Lewis base may be performed while changing the temperature in the middle, and is preferably performed as such. When changing temperature in the middle of mixing, it is preferable to mix at the temperature of 5-30 degreeC first, and to change the temperature to 30-60 degreeC after that, and to mix. In this way, a thermally stable structure of Lewis acid, water, and Lewis base is formed in the low-temperature process, the insoluble matter is completely dissolved in the high-temperature process, and the Lewis acid is less involved in water. And the mixed state of Lewis base. The initial mixing temperature is more preferably 10 to 25 ° C, and the subsequent mixing temperature is more preferably 40 to 60 ° C.
In that case, it is preferable to perform mixing at the first temperature for 1 to 300 minutes, and then perform mixing after changing the temperature for 1 to 300 minutes.

In the step of mixing the Lewis acid and the Lewis base, the mixing ratio of the Lewis acid and the Lewis base is not necessarily a stoichiometric ratio. That is, any one of Lewis acid and Lewis base (converted to the base point amount) may be contained in excess of the theoretical amount (equivalent).
That is, the mixing ratio of Lewis acid and Lewis base in the cation curing catalyst is the ratio of the number of atoms n (b) of the Lewis base point to the number of boron atoms n (a) of the Lewis acid point (n ( b) / n (a)), even if it is not 1 (stoichiometric ratio), it acts as a cationic curing catalyst.
The ratio n (b) / n (a) in the cationic curing catalyst affects the storage stability and cationic curing characteristics (curing speed, degree of curing of the cured product, etc.) of the resin composition.
In the case where the Lewis base has two Lewis base points in the molecule, such as diamines, the ratio n is determined when the mixing molar ratio of the Lewis base to the Lewis acid constituting the cationic curing catalyst is 0.5. (B) / n (a) = 1 (stoichiometric ratio). In this way, the ratio n (b) / n (a) is calculated.

From the viewpoint of the storage stability of the resin composition containing the cationic curing catalyst, if the Lewis acid is present in an excessive amount relative to the Lewis base, the storage stability may be lowered, so that the resin composition is more excellent in storage stability. Therefore, the ratio n (b) / n (a) is preferably 0.5 or more. For the same reason, the ratio is more preferably 0.8 or more, still more preferably 0.9 or more, still more preferably 0.95 or more, and particularly preferably 0.99 or more.
On the other hand, from the viewpoint of cationic curing characteristics, if the Lewis base is excessively large, the low-temperature curability of the cured product may be reduced, so that the composition is also excellent in cationic curing characteristics when the resin composition is cured. It is preferable that n (b) / n (a) is 100 or less. For the same reason, the ratio n (b) / n (a) is more preferably 20 or less, still more preferably 10 or less, and particularly preferably 5 or less.
Furthermore, from the viewpoint of cationic curing properties, a Lewis base is composed of a compound having a nitrogen atom, a sulfur atom or a phosphorus atom, and is a structure having two or more carbon substitutions (a structure having two or more carbon substitutions is a carbon atom in these atoms. The ratio n (b) / n (a) is preferably 2 or less because the acid dissociation constant is high and the steric hindrance is large. , 1.5 or less is more preferable, and 1.2 or less is still more preferable. For example, in a structure such as a hindered amine, the above range is preferable.
Further, when the Lewis base is ammonia or a low-boiling amine having a small steric hindrance, the ratio n (b) / n (a) is preferably larger than 1 particularly when ammonia is used. Specifically, it is preferably 1.001 or more, more preferably 1.01 or more, still more preferably 1.1 or more, and particularly preferably 1.5 or more.

The cationic curing catalyst obtained by the method for producing a cationic curing catalyst according to the present invention includes a Lewis acid (organic borane) represented by the above general formula (1) and a Lewis base. Since cationic curing can be employed, the resulting cured product is particularly resistant to heat, chemical stability, moisture resistance, etc., compared to the case where addition type curing such as acid anhydride curing is employed. It has excellent characteristics required for the application. Compared to the case of using a conventional cationic curing catalyst such as antimony-based sulfonium salt, coloring due to heat (heat at the time of curing, usage environment) is reduced, moisture absorption is low, heat and moisture resistance and UV irradiation resistance A cured product having excellent durability such as the above can be obtained. In addition, the mold releasability of the cured product is excellent. And by manufacturing such a cation curing catalyst with the manufacturing method of this invention, the resin composition using a cation curing catalyst becomes the thing which was further excellent in storage stability.
Such a cationic curing catalyst obtained by the method for producing a cationic curing catalyst of the present invention is also one aspect of the present invention.
A cation curable resin composition comprising the cation curable catalyst of the present invention and a cation curable compound is also one aspect of the present invention.
As described above, since the cationic curing catalyst of the present invention is one in which coloring of the cured product of the resin composition caused by the catalyst is suppressed, the cationic curing resin composition of the present invention is suitable for optical material applications. Can be used.
The presence or absence or degree of coloring of the cured product based on the catalyst used can be usually confirmed from the change in transmittance at 400 nm. That is, by measuring the transmittance of the cured product at 400 nm, it is possible to evaluate the presence / absence and degree of coloring of the cured product.
The cationic curing catalyst is a catalyst that accelerates the cationic curing reaction, and functions differently from, for example, a curing accelerator in an acid anhydride curing reaction.

R in the said General formula (1) is the same or different, and represents the hydrocarbon group which may have a substituent. Although the said hydrocarbon group is not specifically limited, It is preferable that it is a C1-C20 hydrocarbon group. The hydrocarbon group having 1 to 20 carbon atoms is not limited as long as it has 1 to 20 carbon atoms as a whole, but is preferably an alkyl group, an aryl group, or an alkenyl group. The alkyl group, aryl group, and alkenyl group may be an unsubstituted group or a group in which one or more hydrogen atoms are substituted with another organic group or a halogen atom. Other organic groups in this case include an alkyl group (when the hydrocarbon group represented by R is an alkyl group, the substituted hydrocarbon group corresponds to an unsubstituted alkyl group as a whole), An aryl group, an alkenyl group, an alkoxy group, a hydroxyl group, etc. are mentioned.

X in the said General formula (1) is an integer of 1-5, and is the same or different and represents the number of the fluorine atoms couple | bonded with the aromatic ring. The bonding position of the fluorine atom in the aromatic ring is not particularly limited. x is preferably 2 to 5, more preferably 3 to 5, and most preferably 5.
Further, a is an integer of 1 or more, b is an integer of 0 or more, and a + b = 3 is satisfied. That is, the Lewis acid is one in which at least one aromatic ring to which a fluorine atom is bonded is bonded to a boron atom. a is more preferably 2 or more, and most preferably 3, that is, a form in which three aromatic rings to which fluorine atoms are bonded are bonded to boron atoms.

Specific examples of the Lewis acid include tris (pentafluorophenyl) borane (TPB), bis (pentafluorophenyl) phenylborane, pentafluorophenyl-diphenylborane, and tris (4-fluorophenyl) borane. TPB is more preferable because it can improve the heat resistance, moisture heat resistance, low water absorption, UV irradiation resistance and the like of the molded body.
In addition, in this specification, an Example, etc., what contains TPB as a Lewis acid among the cationic curing catalysts concerning this invention may be described as a TPB type catalyst.
TPB can be synthesized by the method described in International Publication No. WO1997 / 031924.

The Lewis base is not limited as long as it can be coordinated to the Lewis acid, that is, can form a coordinate bond with the boron atom of the Lewis acid, and those commonly used as Lewis bases are used. However, compounds having atoms with lone pairs are preferred. Specifically, a compound having a nitrogen atom, a phosphorus atom or a sulfur atom is preferred. In this case, the Lewis base forms a coordinate bond by donating a non-shared electron pair possessed by a nitrogen atom, a phosphorus atom, or a sulfur atom to the boron atom of the Lewis acid. Moreover, the compound which has a nitrogen atom or a phosphorus atom is more preferable.
Preferred examples of the compound having a nitrogen atom include amines (monoamines and polyamines) and ammonia. More preferred are amines having a hindered amine structure, amines having a low boiling point, and ammonia, and still more preferred are polyamines having a hindered amine structure and ammonia. When a polyamine having a hindered amine structure is used as the Lewis base, the cured molded article can be prevented from oxidation due to the radical scavenging effect, and the resulting cured product has excellent heat resistance (wet heat resistance). On the other hand, when ammonia or a low-boiling amine is used as the Lewis base, the resulting cured product is excellent in low water absorption and UV irradiation resistance. The ammonia or low boiling point amine volatilizes in the curing process, so that the salt structure derived from ammonia or the low boiling point amine in the final molded product (cured product) is reduced, so the water absorption rate of the molded product is reduced. It is speculated that it can. In particular, ammonia is preferable because of its excellent effects.

As the amine having the hindered amine structure, a nitrogen atom forming a coordinate bond with a boron atom constitutes a secondary or tertiary amine from the viewpoint of storage stability of the resin composition and curability at the time of molding. It is preferable that it is polyamine more than diamine. Specific examples of the amine having a hindered amine structure include 2,2,6,6-tetramethylpiperidine, N-methyl-2,2,6,6-tetramethylpiperidine; TINUVIN770, TINUVIN765, TINUVIN144, TINUVIN123, and TINUVIN744. CHIMASSORB2020FDL (manufactured by BASF); ADK STAB LA-52, ADK STAB LA-57 (manufactured by ADEKA) and the like. Among them, TINUVIN770, TINUVIN765, Adekastab LA-52, and Adekastab LA-57 having two or more hindered amine structures per molecule are preferable.

As the low boiling point amine, it is preferable to use an amine having a boiling point of 120 ° C. or lower, more preferably 80 ° C. or lower, still more preferably 50 ° C. or lower, still more preferably 30 ° C. or lower, particularly preferably. Is 5 ° C. or lower. Specifically, primary amines such as monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, ethylenediamine; secondary amines such as dimethylamine, diethylamine, dipropylamine, methylethylamine, piperidine; And tertiary amines such as trimethylamine and triethylamine.

The compound having a phosphorus atom is preferably a phosphine. Specific examples include triphenylphosphine, trimethylphosphine, tritoluylphosphine, methyldiphenylphosphine, 1,2-bis (diphenylphosphino) ethane, and diphenylphosphine.

Preferred examples of the compound having a sulfur atom include thiols and sulfides. Specific examples of thiols include methyl thiol, ethyl thiol, propyl thiol, hexyl thiol, decane thiol, and phenyl thiol. Specific examples of the sulfides include diphenyl sulfide, dimethyl sulfide, diethyl sulfide, methylphenyl sulfide, methoxymethylphenyl sulfide and the like.

Specific examples of the cationic curing catalyst in the present invention include TPB / monoalkylamine complexes, TPB / dialkylamine complexes, TPB alkylamine complexes such as TPB / trialkylamine complexes, and organic borane / amine complexes such as TPB / hindered amine complexes. Organic borane / ammonia complex such as TPB / NH ₃ complex; organic borane / phosphine complex such as TPB / triarylphosphine complex, TPB / diarylphosphine complex, TPB / monoarylphosphine complex; organic borane such as TPB / alkylthiol complex / Orthiol complex; Organic borane / sulfide complex such as TPB / diaryl sulfide complex and TPB / dialkyl sulfide complex. Of these, TPB / alkylamine complexes, TPB / hindered amine complexes, TPB / NH ₃ complexes, and TPB / phosphine complexes are preferred.

In the cation curable resin composition of the present invention, the content of the cation curing catalyst is an amount of an active ingredient not containing a solvent or the like (total amount of Lewis acid and Lewis base represented by the general formula (1)). It is suitable to set it as 0.01-10 mass parts with respect to 100 mass parts of cationic curable compounds mentioned later. If the amount is less than 0.01 parts by mass, the curing rate may not be sufficiently increased when the resin composition is cured. More preferably, it is 0.05 mass part or more, More preferably, it is 0.1 mass part or more. Further, if the amount exceeds 10 parts by mass, there is a risk of coloring at the time of curing or heating of the molded article, so from the viewpoint of colorlessness and transparency, it is preferably 10 parts by mass or less. More preferably, it is 5 mass parts or less, More preferably, it is 3 mass parts or less, Most preferably, it is 2 mass parts or less.

In the cationic curable resin composition, the cationic curable compound (also referred to as “cationic curable resin”) may be any compound that can be cured (polymerized) by a cationic curing reaction, and may be an epoxy group, an oxetane group (an oxetane ring). ), A compound having a cationically curable functional group such as a dioxolane group, a trioxane group, a vinyl group, a vinyl ether group, or a styryl group. Among these, an epoxy compound having an epoxy group and an oxetane compound having an oxetane group are more preferable.
In addition, the “epoxy group” in the present specification includes an oxirane ring which is a three-membered ether, and in addition to a strict epoxy group, a group in which the oxirane ring is bonded to carbon, such as a glycidyl group. And a group containing an ether or ester bond such as a glycidyl ether group and a glycidyl ester group, an epoxycyclohexane ring, and the like.

As the epoxy compound, an alicyclic epoxy compound, a hydrogenated epoxy compound, an aromatic epoxy compound, and an aliphatic epoxy compound are preferable, and an alicyclic epoxy compound and a hydrogenated epoxy compound are more preferable. A seed may be used and two or more kinds may be mixed and used.
Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, epsilon-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexane. Epoxy compounds having an epoxycyclohexane group such as carboxylate and bis- (3,4-epoxycyclohexyl) adipate; 1,2-epoxy-4- (2-oxiranyl) of 2,2-bis (hydroxymethyl) -1-butanol ) Alicyclic epoxides other than epoxy compounds having an epoxycyclohexane group, such as cyclohexane adducts and epoxy resins containing heterocycles such as triglycidyl isocyanurate.

The hydrogenated epoxy compound is preferably a compound having a glycidyl ether group bonded directly or indirectly to a saturated aliphatic cyclic hydrocarbon skeleton, and a polyfunctional glycidyl ether compound is preferred. Such a hydrogenated epoxy compound is preferably a complete or partial hydrogenated product of an aromatic epoxy compound, more preferably a hydrogenated product of an aromatic glycidyl ether compound, and still more preferably an aromatic polyfunctional compound. It is a hydrogenated product of a glycidyl ether compound. Specifically, hydrogenated bisphenol A type epoxy compounds, hydrogenated bisphenol S type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, and the like are preferable. More preferred are hydrogenated bisphenol A type epoxy compounds and hydrogenated bisphenol F type epoxy compounds.

Preferred examples of the aromatic epoxy compound include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, fluorene type epoxy compounds, and aromatic epoxy compounds having a bromo substituent. Of these, bisphenol A type epoxy compounds and fluorene type epoxy compounds are preferred.
Also, aromatic glycidyl ether compounds such as epibis type glycidyl ether type epoxy resins, high molecular weight epibis type glycidyl ether type epoxy resins, novolak aralkyl type glycidyl ether type epoxy resins and the like can be suitably used.

The aliphatic epoxy compound is preferably an aliphatic glycidyl ether type epoxy resin. Examples of the aliphatic glycidyl ether type epoxy resin include polyhydroxy compounds (ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (PEG 600), propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, Polypropylene glycol (PPG), glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and multimers thereof, pentaerythritol and multimers thereof, mono / polysaccharides such as glucose, fructose, lactose, maltose, etc.) and epihalohydrin Preferred examples include those obtained by the condensation reaction. Among these, aliphatic glycidyl ether type epoxy resins having a propylene glycol skeleton, an alkylene skeleton, and an oxyalkylene skeleton as the central skeleton are more preferable.

The oxetane compound is a compound having an oxetane group (oxetane ring), and any of a monofunctional oxetane compound having one oxetane group and a polyfunctional oxetane compound having two or more oxetane groups can be used.

Among the above cationic curable compounds, alicyclic epoxy compounds and hydrogenated epoxy compounds are particularly suitable. These are less likely to cause coloration of the epoxy compound itself during curing, and are less likely to be colored or deteriorated by light, that is, excellent in transparency, low colorability, and light resistance. Therefore, if it is set as the resin composition containing these, the optical member which is excellent in light resistance without coloring can be obtained with high productivity. Thus, the form in which the said cationic curable compound contains at least 1 sort (s) selected from the group which consists of an alicyclic epoxy compound and a hydrogenated epoxy compound is also one of the suitable forms of this invention.

In the form in which the cationic curable compound includes at least one selected from the group consisting of an alicyclic epoxy compound and a hydrogenated epoxy compound, the content of the alicyclic epoxy compound and the hydrogenated epoxy compound is the sum of these. The amount is preferably 50% by mass or more based on 100% by mass of the total amount of the cationic curable compound. As a result, it is possible to further exert the effects of using the above-described alicyclic epoxy compound or hydrogenated epoxy compound. More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more.

The cationic curable resin composition of the present invention may contain a release agent.
Specifically, a compound having an alcoholic OH group and / or a carbonyl group (including a carboxyl group and an ester group) is preferable as the mold release agent, and the compatibility with the cationic curable resin composition and the mold release effect are high. From the viewpoint, those having a hydrocarbon group having 8 or more carbon atoms are preferred. More preferably, an alcohol having 8 to 36 carbon atoms, a carboxylic acid having 8 to 36 carbon atoms, a carboxylic acid ester having 8 to 36 carbon atoms, a carboxylic acid anhydride having 8 to 36 carbon atoms, and a carboxylic acid having 8 to 36 carbon atoms. It is at least one compound selected from the group consisting of salts. By containing such a mold release agent, it can be cured in a short time, and the mold can be easily peeled off when cured using a mold, and the appearance can be obtained without damaging the surface of the cured product. It is possible to control and develop transparency. Therefore, the resin composition can be made more useful for electric / electronic component material use, optical member use, and the like.

When the release agent is included, the content is preferably 10% by mass or less with respect to 100% by mass of the resin composition. If it exceeds 10% by mass, the resin composition may be hard to be cured. More preferably, it is 0.01-5 mass%, More preferably, it is 0.1-2 mass%.

The cationic curable resin composition of the present invention may further contain a flexible component (flexible component) for increasing the toughness of the resin composition, an inorganic material, a dye, and the like.
In addition, as long as the effects of the present invention are not impaired, a curing catalyst / curing agent other than a cationic curing catalyst, a curing accelerator, a reactive diluent, a saturated compound having no unsaturated bond, a pigment, a dye, an antioxidant Adhesives such as agents, ultraviolet absorbers, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization inhibitors, inorganic fillers, organic fillers, coupling agents, etc. Improving agent, heat stabilizer, antibacterial / antifungal agent, flame retardant, matting agent, antifoaming agent, leveling agent, wetting / dispersing agent, anti-settling agent, thickener / anti-sagging agent, anti-coloring agent, An emulsifier, an anti-slip / scratch agent, an anti-skinning agent, a drying agent, an antifouling agent, an antistatic agent, a conductive agent (electrostatic aid), a solvent and the like may be contained.

The cation curable resin composition of the present invention can be prepared by mixing the cation curable compound and the cation curable catalyst, and mixing the other components as necessary.
Moreover, when mixing each component, each component or mixture can also be heated and mixed so that it may become a uniform composition as needed. The heating temperature is not particularly limited as long as it is not higher than the decomposition temperature of the curable resin or not higher than the reaction temperature, but is preferably 140 to 20 ° C, more preferably 120 to 40 ° C before addition of the catalyst.

The cation curable resin composition preferably has a viscosity of 10,000 Pa · s or less. Thereby, it is excellent in processing characteristics, for example, it is more excellent for a molded body forming application (particularly for forming a mold molded body). More preferably, it is 1000 Pa.s or less, More preferably, it is 200 Pa.s or less. Moreover, it is preferable that it is 0.01 Pa.s or more, and it is more preferable that it is 0.1 Pa.s or more. More preferably, it is 1 Pa · s or more, more preferably 5 Pa · s or more, and particularly preferably 10 Pa · s or more.
The measurement of the viscosity can be performed on the resin composition using an R / S rheometer (manufactured by Brookfield, USA) under the conditions of 40 ° C. and rotation speed D = 1 / s. An RC25-1 measuring jig can be used at a viscosity of 20 Pa · s or more, and an RC50-1 jig can be used at a viscosity of less than 20 Pa · s. Moreover, about the thing whose viscosity at the rotational speed D = 1 / s cannot be measured, the value of rotational speed D = 5-100 / s can be extrapolated and it can evaluate as a viscosity of a resin composition.

As a method for curing the resin composition, various methods such as thermosetting and photocuring (curing by irradiation with active energy rays) can be suitably used. As thermosetting, it is preferable to cure at about 30 to 400 ° C., and as photocuring, it is preferable to cure at 10 to 10,000 mJ / cm ² . Curing may be performed in one stage, or may be performed in two stages such as primary curing (preliminary curing) and secondary curing (main curing). For example, when molding such as a lens is required, a demolding operation is required. However, a primary curing is performed before the demolding operation and a secondary curing is performed after the demolding operation. -A molding method is preferably employed.
Hereinafter, the case of performing the two-stage curing will be described in detail.
As a two-step curing method, as a first step corresponding to primary curing, the resin composition is photocured at 10 to 100000 mJ / cm ² or thermally cured at 80 to ²⁰⁰ ° C., and the first step It is preferable to employ a method including a second step corresponding to the secondary curing in which the cured product obtained in the step is thermally cured at a temperature exceeding 200 ° C. and not exceeding 500 ° C.

In the said 1st process, in the case of thermosetting, it is preferable to make hardening temperature into 80-200 degreeC. More preferably, it is 100 degreeC or more and 160 degrees C or less. Moreover, you may change a curing temperature in steps within the range of 80-200 degreeC.
The curing time in the thermosetting step is preferably, for example, within 10 minutes, more preferably within 5 minutes, and even more preferably within 3 minutes. Further, it is preferably 10 seconds or longer, more preferably 30 seconds or longer.

The thermosetting step can also be performed in air or in an atmosphere of an inert gas such as nitrogen, under reduced pressure, or under pressure. For example, from the standpoint of improving productivity, etc., the resin composition is kept in the mold at a predetermined temperature and time, and then taken out of the mold and left in the atmosphere of an inert gas such as nitrogen or in a heat treatment. It is also possible to do. Moreover, you may combine photocuring (curing by active energy ray irradiation).

The first step is also preferably a curing step using a mold made of metal, ceramic, glass, resin or the like (referred to as “mold”). The curing process using a mold may be a curing process normally performed in a mold molding method such as an injection molding method, a compression molding method, a casting molding method, a sandwich molding method, etc., but the first step is If it is a hardening process using such a metal mold | die, it is excellent in various physical properties, such as abrasion resistance, a low shrinkage, a dimensional accuracy, and mold transfer property, and it can manufacture easily a transparent molded object without coloring. .

When the first step is a curing step using a mold, it is preferable to perform the demolding step after the first step and before the second step. The mold including the demolding process, that is, the cured product obtained in the first process is taken out from the mold, and the taken cured product is used for the next second process, whereby the expensive mold is effectively rotated (recycled). ) And the life of the mold can be extended, and a molded product can be obtained at low cost.
In this case, the resin composition is a one-component composition containing a curing agent and other components as necessary, and the one-component composition is filled into a mold that matches the shape of the target molded article (injection / A method in which the cured product is taken out from the mold after coating and the like is suitably used.

In the curing method, in the second step, the cured product obtained in the first step (preferably, the cured product taken out from the mold by the demolding step) is heat-cured at a temperature exceeding 200 ° C. and not more than 500 ° C. preferable. The lower limit of the curing temperature is more preferably 250 ° C. or higher, still more preferably 300 ° C. or higher, particularly preferably 330 ° C. or higher, and most preferably 350 ° C. or higher. The upper limit is more preferably 400 ° C. or lower. Further, the curing temperature may be changed stepwise within a temperature range exceeding 200 ° C. and not more than 500 ° C.
The curing time in the second step is not particularly limited as long as the curing rate of the obtained molded body is sufficient, but considering production efficiency, for example, 30 minutes to 30 hours is preferable. . More preferably, it is 1 to 10 hours.

The second step can also be performed in any atmosphere such as air or an inert gas atmosphere such as nitrogen. In particular, the second step is preferably performed in an atmosphere having a low oxygen concentration. For example, it is preferable to carry out in an inert gas atmosphere having an oxygen concentration of 10% by volume or less. More preferably, it is 3 volume% or less, More preferably, it is 1 volume% or less, Especially preferably, it is 0.5 volume% or less, Most preferably, it is 0.3 volume% or less.

As described above, the cationic curable resin composition of the present invention can give a molded article excellent in heat resistance, moisture and heat resistance, low water absorption, UV irradiation resistance and the like. Thus, a molded article (cured product) obtained by curing the cationic curable resin composition of the present invention is also one aspect of the present invention.
The molded body is useful for various applications such as optical materials (members), mechanical component materials, electrical / electronic component materials, automotive component materials, civil engineering and building materials, molding materials, paint materials, and adhesive materials. Is. Especially, it can use suitably for an optical material, an optical device member, a display device member, etc. Specific examples of such applications include eyeglass lenses, (digital) cameras, camera cameras for mobile phones, in-vehicle cameras, and other camera imaging lenses, light beam condensing lenses, light diffusion lenses, and other lenses, LEDs. Optical applications such as sealing materials, optical adhesives, optical transmission bonding materials, filters, diffraction gratings, prisms, light guides, watch glasses, transparent glasses such as cover glasses for display devices, and cover glasses; photo sensors, Opto device applications such as photoswitches, LEDs, light emitting elements, optical waveguides, multiplexers, duplexers, disconnectors, optical splitters, optical fiber adhesives; substrates for display elements such as LCD, organic EL and PDP, color Display devices such as filter substrates, touch panel substrates, display protective films, display backlights, light guide plates, antireflection films, and antifogging films Applications and the like are suitable.
In addition, when the said resin composition is a resin composition for optical materials, according to the use of an optical material, the other component may be included suitably. Specific examples of other components include UV absorbers, IR cut agents, reactive diluents, pigments, washing agents, antioxidants, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, heat transfer agents, Preferable examples include a polymerization initiator, an anaerobic polymerization initiator, a polymerization inhibitor, and an antifoaming agent.

The method for producing a cationic curable catalyst of the present invention comprises the above-described configuration, and a cation curable catalyst capable of improving the storage stability of the cation curable resin composition can be produced by a simple method. A cation curable resin composition containing a cation curing catalyst produced by the production method of the present invention, which is a useful method, is an optical material (member), a machine part material, an electric / electronic part material, an automobile part material, a civil engineering building. It can use suitably for various uses, such as a material and a molding material.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

Synthesis Example 1 (Synthesis of TPB-containing powder A)
According to the synthesis method described in International Publication No. WO1997 / 031924, 189 g of an Isopar E (manufactured by ExxonMobil) solution having a tris (pentafluorophenyl) boron (hereinafter also referred to as TPB) content of 7% was prepared. To this solution, 2.22 g of γ-butyrolactone was added dropwise at 60 ° C. White crystals precipitated from the middle of the dropping. After cooling the reaction solution to room temperature, the resulting slurry was suction filtered and washed with n-heptane. The obtained cake was dried at 40 ° C. under reduced pressure, and 14.1 g of white crystals of TPB · γ-butyrolactone complex (TPB-containing powder A) was obtained. This complex had a γ-butyrolactone concentration of 13.2% (GC analysis), a water content of 0.3% (Karl Fischer moisture meter), and a TPB content of 86.5%. ^No peaks other than TPB, γ-butyrolactone, and water were detected in ¹ H-NMR, ¹⁹ F-NMR analysis, and GC analysis. The measurement results of ¹ H-NMR and ¹⁹ F-NMR were as follows.
¹ H-NMR (CDCl ₃ ) ppm (standard substance: TMS 0 ppm)
δ = 2.44 (2H, m) γ-butyrolactone δ = 2.83 (2H, t) γ-butyrolactone δ = 4.46 (2H, t) γ-butyrolactone δ = 8.74 (2H, s) water
¹⁹ F-NMR (CDCl ₃ ) ppm (standard substance: CFCl ₃ 0 ppm)
δ = −135.5 (6F, m)
δ = -156.9 (3F, dd)
δ = -163.9 (6F, d)

Synthesis Example 2 (Synthesis of TPB-containing powder B)
According to the synthesis method described in International Publication No. WO1997 / 031924, 255 g of an Isopar E solution having a TPB content of 7% was prepared. Water was added dropwise to this solution at 60 ° C. White crystals precipitated from the middle of the dropping. After cooling the reaction solution to room temperature, the resulting slurry was suction filtered and washed with n-heptane. The obtained cake was dried at 60 ° C. under reduced pressure, and 18.7 g of TPB / water complex (TPB-containing powder B) as white crystals was obtained. This complex had a water content of 9.2% (Karl Fischer moisture meter) and a TPB content of 90.8%. The complex after drying was subjected to ¹⁹ F-NMR analysis and GC analysis, but no peaks other than TPB were detected.
The measurement result of ¹⁹ F-NMR was as follows.
¹⁹ F-NMR (CDCl ₃ ) ppm (standard substance: CFCl ₃ 0 ppm)
δ = −135.6 (6F, m)
δ = -156.5 (3F, dd)
δ = −163.5 (6F, d)

The results of component analysis of the TPB-containing powders A and B synthesized in Synthesis Examples 1 and 2 were as follows.
TPB-containing powder A:
TPB 86.5% by mass, water 0.3% by mass, γ-butyrolactone 13.2% by mass
TPB-containing powder B:
TPB 90.8 mass%, water 9.2 mass%

Example 1
2.2 g of γ-butyrolactone was added to 2 g of TPB-containing powder A ((TPB pure content: 1.73 g, 3.379 mmol), (water: 0.006 g, 0.333 mmol)), and 10 minutes at room temperature. After mixing, 0.741 g of ADK STAB LA-57 was added, mixed at room temperature for 10 minutes, and further mixed at 60 ° C. for 20 minutes to obtain a uniform solution of a cationic curing catalyst (TPB catalyst).

Example 2
0.02 g (1.110 mmol) of water and γ-butyrolactone with respect to 2 g of TPB-containing powder A ((TPB pure content: 1.73 g, 3.379 mmol), (water: 0.006 g, 0.333 mmol)) After adding 2.2 g of the mixture and mixing at room temperature for 10 minutes, 0.741 g of ADK STAB LA-57 was added, mixed at room temperature for 10 minutes, and further mixed at 60 ° C. for 20 minutes to prepare a cationic curing catalyst (TPB catalyst). A homogeneous solution was obtained.

Comparative Example 1
TPB-containing powder A 2 g ((TPB pure content: 1.73 g, 3.379 mmol), (water: 0.006 g, 0.333 mmol)), 0.1 g (5.549 mmol) of water, γ-butyrolactone After adding 2.1 g of the mixture and mixing at room temperature for 10 minutes, 0.741 g of ADK STAB LA-57 was added, mixed at room temperature for 10 minutes, and further mixed at 60 ° C. for 20 minutes, and the cationic curing catalyst (TPB catalyst) A homogeneous solution was obtained.

Example 3
TPB-containing powder A 2 g ((TPB pure content: 1.73 g, 3.379 mmol), (water: 0.006 g, 0.333 mmol)), 0.01 g (0.555 mmol) of water, γ-butyrolactone After adding 2.1 g of the mixture and mixing at room temperature for 10 minutes, 0.741 g of ADK STAB LA-57 was added, mixed at room temperature for 10 minutes, and further mixed at 60 ° C. for 20 minutes, and the cationic curing catalyst (TPB catalyst) A homogeneous solution was obtained.

Example 4
TPB-containing powder A 2 g ((TPB pure content: 1.73 g, 3.379 mmol), (water: 0.006 g, 0.333 mmol)), 0.015 g (0.832 mmol) of water, γ-butyrolactone After adding 2.1 g of the mixture and mixing at room temperature for 10 minutes, 0.741 g of ADK STAB LA-57 was added, mixed at room temperature for 10 minutes, and further mixed at 60 ° C. for 20 minutes, and the cationic curing catalyst (TPB catalyst) A homogeneous solution was obtained.

Example 5
TPB-containing powder A 2 g ((TPB pure content: 1.73 g, 3.379 mmol), (water: 0.006 g, 0.333 mmol)), 0.025 g (1.387 mmol) of water, γ-butyrolactone After adding 2.1 g of the mixture and mixing at room temperature for 10 minutes, 0.741 g of ADK STAB LA-57 was added, mixed at room temperature for 10 minutes, and further mixed at 60 ° C. for 20 minutes, and the cationic curing catalyst (TPB catalyst) A homogeneous solution was obtained.

Comparative Example 2
TPB-containing powder A 2 g ((TPB pure content: 1.73 g, 3.379 mmol), (water: 0.006 g, 0.333 mmol)), 0.03 g (1.665 mmol) of water, γ-butyrolactone After adding 2.1 g of the mixture and mixing at room temperature for 10 minutes, 0.741 g of ADK STAB LA-57 was added, mixed at room temperature for 10 minutes, and further mixed at 60 ° C. for 20 minutes, and the cationic curing catalyst (TPB catalyst) A homogeneous solution was obtained.

Comparative Example 3
TPB-containing powder A 2 g ((TPB pure content: 1.73 g, 3.379 mmol), (water: 0.006 g, 0.333 mmol)), 0.04 g (2.22 mmol) of water, γ-butyrolactone After adding 2.1 g of the mixture and mixing at room temperature for 10 minutes, 0.741 g of ADK STAB LA-57 was added, mixed at room temperature for 10 minutes, and further mixed at 60 ° C. for 20 minutes, and the cationic curing catalyst (TPB catalyst) A homogeneous solution was obtained.

Comparative Example 4
TPB-containing powder A 2 g ((TPB pure content: 1.73 g, 3.379 mmol), (water: 0.006 g, 0.333 mmol)), 0.055 g (3.052 mmol) of water, γ-butyrolactone After adding 2.1 g of the mixture and mixing at room temperature for 10 minutes, 0.741 g of ADK STAB LA-57 was added, mixed at room temperature for 10 minutes, and further mixed at 60 ° C. for 20 minutes, and the cationic curing catalyst (TPB catalyst) A homogeneous solution was obtained.

Comparative Example 5
0.075 g (4.162 mmol) of water and γ-butyrolactone with respect to 2 g of TPB-containing powder A ((TPB pure content: 1.73 g, 3.379 mmol), (water: 0.006 g, 0.333 mmol)) After adding 2.1 g of the mixture and mixing at room temperature for 10 minutes, 0.741 g of ADK STAB LA-57 was added, mixed at room temperature for 10 minutes, and further mixed at 60 ° C. for 20 minutes, and the cationic curing catalyst (TPB catalyst) A homogeneous solution was obtained.

Comparative Example 6
2.1 g of γ-butyrolactone was added to 2 g of TPB-containing powder B ((TPB pure content: 1.816 g, 3.547 mmol), (water: 0.184 g, 10.2111 mmol)), and 10 minutes at room temperature. After mixing, 0.778 g of ADK STAB LA-57 was added, mixed for 10 minutes at room temperature, and further mixed for 20 minutes at 60 ° C. to obtain a uniform solution of a cation curing catalyst (TPB catalyst).

Preparation of cationic curable resin composition 1 70 g of hydrogenated epoxy resin (YX-8034, manufactured by Mitsubishi Chemical Corporation), 30 g of alicyclic epoxy resin (CELL-2021P, manufactured by Daicel Chemical Industries), and 80 g of stearic acid Mixed at ° C. Then, it cooled to 40 degreeC, 0.5 g of TPB catalyst solutions of Example 1 were mixed, and the cationic curable resin composition 1 was prepared.

Preparation of cationic curable resin composition 2 70 g of hydrogenated epoxy resin (YX-8034, manufactured by Mitsubishi Chemical), 30 g of alicyclic epoxy resin (CELL-2021P, manufactured by Daicel Chemical Industries), and 80 g of stearic acid Mixed at ° C. Then, it cooled to 40 degreeC, the TPB catalyst solution of Example 1 and the water 0.01g were mixed, and the cation curable resin composition 2 was prepared.

Preparation of cationic curable resin compositions 3-6 Cationic curing in the same manner as in the cationic curable resin composition 1 except that the TPB catalyst solution of Examples 2-5 was used instead of the TPB catalyst solution of Example 1. Resin compositions 3 to 6 were prepared.

Preparation of Comparative Cationic Curable Resin Compositions 1-6 70 g of hydrogenated epoxy resin (YX-8034), 30 g of alicyclic epoxy resin (CELL-2021P), and 0.5 g of stearic acid were mixed at 80 ° C. Then, it cooled to 40 degreeC and mixed the TPB catalyst solution 0.5g of the comparative example 1 and the comparative cation curable resin composition 1 was prepared.
Comparative cation curable resin compositions 2 to 6 were prepared in the same manner as the comparative cation curable resin composition 1 except that the TPB catalyst solutions of Comparative Examples 2 to 6 were used instead of the TPB catalyst solution of Comparative Example 1, respectively. did.

About the cation curable resin compositions 1-6 and the comparative cation curable resin compositions 1-6, the hardening characteristic was evaluated with the following method. Moreover, these resin compositions were stored in a state of 45 ° C., and the viscosity immediately after setting to 45 ° C. (after 0 hour), after 2 hours, after 6 hours, and after 8 hours was measured by the following method. Further, these resin compositions were cured by the following curing step, and the obtained cured products were examined for glass transition temperature and cured product transmittance (colored presence / absence) by the following methods. The results are shown in Table 1.
<Curing characteristics>
16 g of the resin composition is collected in a sample bottle (manufactured by Maruemu Co., Ltd., screw tube No. 7), stored in a dryer at 35 ° C. for 30 minutes, and adjusted to 35 ° C.
A temperature sensor is installed at the center of the sample.
An oil bath at 135 ° C. is prepared, and the sample bottle is set in the oil bath so that the resin liquid level in the sample bottle is 10 mm below the liquid level of the oil bath.
The sensor in the resin is monitored, and the time (second) to reach 50 ° C. to 180 ° C. is evaluated as the curing property.
<Viscosity measurement>
The viscosity of the resin composition at 40 ° C. was measured with an E type viscometer TV-22 type coplate type (manufactured by Toki Sangyo Co., Ltd., measurement range H, 3 ° × R9.7, preheat: 120 s, measurement: 180 s). Viscosity measurement was performed immediately after resin adjustment and after storage at 45 ° C. for 2 hours and 8 hours.

<Curing process>
(First step)
Using two metal plates made of SUS304 (manufactured by Nippon Test Panel Co., Ltd., surface No. 800), gaps at intervals of 1000 μm were formed, and each resin composition was cast. After the primary curing at the temperature / time described in Table 1, the mold was removed.
(Second process (cure))
After curing in the first step, curing treatment was performed under the following conditions under N ₂ atmosphere (unless otherwise specified, carried out at an oxygen concentration of 0.2 to 0.3% by volume).
Condition: 250 ° C. × 1 hour (samples are put directly into a dryer at 250 ° C.)
<Glass transition temperature (Tg)>
The primary cured body and the secondary cured body were cut and evaluated by DMA.
<Transmissivity of cured product (presence or absence of coloring)>
The transmittance of the cured product at a wavelength of 400 nm was measured at each time point after the second step (after secondary curing) using an absorptiometer (manufactured by Shimadzu Corporation, spectrophotometer UV-3100).

From the results of Table 1, the resin composition using the cationic curing catalyst of the present invention produced by mixing a Lewis acid and a Lewis base in the presence of water in an amount of less than 55 mol% with respect to the Lewis acid. Compared to a resin composition using a cationic curing catalyst prepared by mixing Lewis acid and Lewis base under a moisture content of 55 mol% or more, the increase in viscosity over time is suppressed and stored. It was confirmed that the resin composition was excellent in stability. Moreover, it was confirmed that the resin composition using the cation curing catalyst of the present invention is excellent in curing characteristics and also suppresses coloring of the cured product.
Further, the resin composition 2 is different from the resin composition 1 in that water is added in an amount of 55 mol% or more with respect to the Lewis acid in the catalyst after preparation of the catalyst, but is equivalent to the resin composition 1. The storage stability was obtained, and the curing characteristics and the coloration of the cured product were the same. From this, it was confirmed that it is meaningful to perform the step of mixing the Lewis acid and the Lewis base in the presence of water in an amount of less than 55 mol% with respect to the Lewis acid.

Claims (5)

A method for producing a cationic curing catalyst comprising the steps of:
The production method comprises the following general formula (1):

(In the formula, R is the same or different and represents a hydrocarbon group which may have a substituent. X is an integer of 1 to 5, and is the same or different and is a fluorine atom bonded to an aromatic ring. A is an integer of 1 or more, b is an integer of 0 or more, and a + b = 3 is satisfied.) The amount of water is less than 55 mol% with respect to the Lewis acid represented by The Lewis acid and the Lewis base are mixed ,
The method for producing a cationic curing catalyst, wherein the Lewis base is a compound having a sulfur atom or a polyamine having a hindered amine structure . The method for producing a cationic curing catalyst according to claim 1, wherein the amount of water is 30 mol% or more based on Lewis acid. The process of mixing the Lewis acid and the Lewis base is performed by first mixing at a temperature of 5 to 30 ° C, and then mixing by changing the temperature to 30 to 60 ° C. A method for producing the cationic curing catalyst as described. Method for producing a cationic curable resin composition characterized by comprising a step of mixing a cationic curing catalyst and a cationic curable compound produced by the production method of the cationic curing catalyst according to claims 1-3. Method for producing a cured product which comprises curing the cationically curable resin composition produced by the production method of cationically curable resin composition according to claim 4.