JP2023052255A - Acid generator, curable composition comprising the acid generator, and cured product thereof - Google Patents

Abstract

To provide an acid generator having excellent solubility in a cation curable compound, and a curable composition that forms a cured product having excellent insulation properties.SOLUTION: An acid generator comprises a salt of a cation represented by the following formula and an anion of a specific structure comprising phosphorus or gallium.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a novel acid generator, a curable composition containing the acid generator, and a cured product thereof.

Conventionally, benzylanilinium salts, for example, are known as compounds (so-called thermal acid generators) that generate acid upon heating to cure cationic curable compounds.

Patent Document 1 discloses a benzylanilinium salt having a cation moiety represented by the following formula and an anion moiety selected from AsF ₆ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ and (C ₆ F ₅ ) ₄ B ⁻ and a sealant for an organic EL display element containing a cationic polymerizable compound.

Japanese Unexamined Patent Application Publication No. 2016-51602

Semiconductor devices are required to have electrical reliability, and contamination with ionic substances must be avoided. Therefore, in a resin-sealed package for a semiconductor element such as an organic EL display element, the sealing resin (cured product of the sealing agent) is required to have electrical insulation.

However, if the acid generator is included in the sealant without being dissolved, not only will it not be possible to obtain the desired curability, but also the insoluble portion of the acid generator will tend to remain in the sealing resin. If the resin contains insoluble matter of the acid generator, it causes deterioration of the electrical characteristics of the semiconductor element.

Furthermore, if the acid generator is contained in the encapsulant without being dissolved, the acid generator will be unevenly distributed in the encapsulating resin. However, there was a problem that it was easily colored. In particular, coloring poses a serious problem when used in optical materials.

In order to solve the above problem, it is important to completely dissolve the acid generator in the resin. Since it is extremely difficult to confirm this, the dissolution of the benzylanilinium salt was ensured by sufficient dissolution work. Therefore, much time was spent on the dissolution work, and work efficiency was poor.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an acid generator having excellent solubility in a cationic curable compound.
Another object of the present invention is to provide a curable composition which is rapidly cured by heat treatment to form a cured product having excellent insulating properties.
Another object of the present invention is to provide a curable composition that can be rapidly cured by heat treatment to form a cured product excellent in heat resistance to yellowing.

The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have found the following matter.
1. Salt (1) of a cation represented by the following formula (c-1) and an anion represented by the following formula (a-1) or (a-2) has excellent solubility in a cationic curable compound. . 3. The resin tends to yellow with acid, but the acid generated by thermal decomposition of the salt (1) hardly causes yellowing of the resin. 4. The use of the salt (1) enables efficient production of a curable composition in which no insoluble matter of the acid generator remains. 5. The curable composition obtained by using the salt (1) has excellent curability and can form a cured product having excellent insulating properties. The present invention is based on these findings that the curable composition obtained by using the salt (1) uniformly contains the acid generator, suppresses uneven distribution of the acid generator, and can form a cured product excellent in heat resistance to yellowing. It is completed based on

（式（ｃ－１）中、Ｒ¹、Ｒ²、Ｒ³は同一又は異なって炭素数１～６のアルキル基を示す。式（ａ－１）中、Ｒ¹¹ｆはフルオロアルキル基を示し、ｓは１～５の整数を示す。式（ａ－２）中、Ｒ¹²ｆは、フルオロアルキル基、又はフルオロアリール基、又はフルオロアルキル置換アリール基を示し、ｔは１～４の整数を示し、ｕは０又は１を示す） That is, the present invention provides an acid generator containing a salt (1) of a cation represented by the following formula (c-1) and an anion represented by the following formula (a-1) or (a-2): offer.

(In formula (c-1), R ¹ , R ² and R ³ are the same or different and represent an alkyl group having 1 to 6 carbon atoms. In formula (a-1), R ¹¹ f represents a fluoroalkyl group. , s represents an integer of 1 to 5. In formula (a-2), R ¹² f represents a fluoroalkyl group, a fluoroaryl group, or a fluoroalkyl-substituted aryl group, and t represents an integer of 1 to 4. and u indicates 0 or 1)

（式（ｃ－２）中、ｎは１以上の整数を示す。Ｒ¹、Ｒ²、Ｒ³は前記に同じである） The present invention further includes a salt (2) of a cation represented by the following formula (c-2) and the anion, wherein the content of the salt (2) is 0.001% by weight or more and 5% by weight % or less.

(In formula (c-2), n represents an integer of 1 or more. R ¹ , R ² and R ³ are the same as above.)

The present invention also provides a curable composition containing the acid generator and a cationic curable compound.

The present invention also provides a cured product of the curable composition.

The acid generator of the present invention has excellent solubility in cationic curable compounds.
Therefore, the acid generator can be completely dissolved only by mixing the acid generator with the cationic curable compound and stirring the mixture for a short period of time, and the curable composition can be produced efficiently.
Moreover, the curable composition obtained by the above method has excellent storage stability, and can suppress precipitation of the acid generator over time.
Furthermore, the curable composition can be rapidly cured by heat treatment to form a cured product having excellent insulating properties.
Furthermore, the cured product of the curable composition uniformly contains the acid generator, or the uneven distribution of the acid generator is suppressed. Furthermore, the acid (H(R ¹¹ f) _s PF _6-s or H([R ¹² f(O) _u ] _t GaF _4-t ) generated by thermal decomposition from the acid generator hardly causes yellowing of the resin. For this reason, the cured product can be prevented from being colored even when exposed to a high-temperature environment, and can stably maintain transparency over a long period of time.

1 shows the results of ¹ H-NMR measurement of salt (1-1a) obtained in Example 1. FIG. 1 is a diagram showing the results of ¹⁹ F-NMR measurement of salt (1-1a) obtained in Example 1. FIG. FIG. 10 shows the results of ¹ H-NMR measurement of salt (1-2a) obtained in Example 21. FIG. 19 shows the results of ¹⁹ F-NMR measurement of salt (1-2a) obtained in Example 21. FIG.

[Acid generator]
The acid generator of the present invention contains a salt (1) of a cation represented by the following formula (c-1) and an anion represented by the following formula (a-1) or (a-2).

The salt (1) includes a salt (1-1) of a cation represented by the formula (c-1) and an anion represented by the formula (a-1), and ) and an anion represented by formula (a-2) above (1-2).

In formula (c-1), R ¹ , R ² and R ³ are the same or different and represent an alkyl group having 1 to 6 carbon atoms.

In formula (a-1), R ¹¹ f represents a fluoroalkyl group, and s represents an integer of 1-5.

In formula (a-2), R ¹² f represents a fluoroalkyl group, a fluoroaryl group, or a fluoroalkyl-substituted aryl group, t represents an integer of 1 to 4, and u represents 0 or 1.

Examples of alkyl groups having 1 to 6 carbon atoms for R ¹ , R ² and R ³ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, A pentyl group, a hexyl group, and the like can be mentioned.

R ¹ is preferably a C _1-4 alkyl group.

R ² and R ³ are preferably C _1-3 alkyl groups, particularly preferably C _1-2 alkyl groups.

As R ¹ , R ² , and R ³ , the following combinations [1] to [3] are preferable from the viewpoint of excellent solubility.
[1] R ¹ is a methyl group, and R ² and R ³ are the same or different and are C _2-4 alkyl groups [2] R ¹ is a C _2-4 alkyl group, and R ² and R ³ are [3] R ¹ , R ² and R ³ which are methyl groups are all methyl groups

The fluoroalkyl group for R ¹¹ f is a group in which at least one hydrogen atom bonded to an alkyl group is substituted with a fluorine atom. Examples of the alkyl group include linear or branched alkyl groups having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms, particularly preferably 2 to 3 carbon atoms, most preferably 2 carbon atoms). be done.

The fluoroalkyl group for R ¹¹ f is preferably a perfluoroalkyl group (=a group in which all hydrogen atoms bonded to the alkyl group are substituted with fluorine atoms), more preferably a perfluoro C _1-5 alkyl group. , a perfluoro C _1-3 alkyl group is particularly preferred, a perfluoro C _2-3 alkyl group is most preferred, and a perfluoroethyl group is particularly preferred.

The s represents an integer of 1 to 5, preferably an integer of 2 to 4, particularly preferably 3.

As the anion represented by the formula (a-1), tris(perfluoroalkyl)trifluorophosphate anion is preferable, and among them, tris(perfluoroethyl)trifluorophosphate anion, tris(perfluoropropyl)trifluoro Phosphate anions, tris(perfluorobutyl)trifluorophosphate anions are preferred, and tris(perfluoroethyl)trifluorophosphate anions (=tris(pentafluoroethyl)trifluorophosphate anions) are particularly preferred.

Examples of the fluoroalkyl group for R ¹² f include the same examples as the fluoroalkyl group for R ¹¹ f.

The fluoroalkyl group for R ¹² f is preferably a perfluoroalkyl group, particularly preferably a perfluoroC _1-5 alkyl group, and most preferably a perfluoroC _1-3 alkyl group.

The fluoroaryl group for R ¹² f is a group in which at least one hydrogen atom bonded to an aryl group is substituted with a fluorine atom. As the aryl group, for example, an aryl group having 6 to 14 carbon atoms such as a phenyl group and a naphthyl group is preferable, and a phenyl group is particularly preferable.

As the fluoroaryl group for R ¹² f, a perfluoroaryl group is preferred, a perfluoro C _6-14 aryl group is particularly preferred, and a perfluorophenyl group is most preferred.

The fluoroalkyl-substituted aryl group for R ¹² f is an aryl group having, as a substituent, a group in which at least one hydrogen atom bonded to an alkyl group is substituted with a fluorine atom. Examples of the alkyl group and the aryl group include the same examples as those described above.

The fluoroalkyl-substituted aryl group for R ¹² f is preferably a perfluoroalkyl-substituted aryl group, more preferably a perfluoro-C _1-5 alkyl-substituted aryl group, and particularly preferably a perfluoro-C _1-3 alkyl-substituted aryl group. , perfluoro C _1-3 alkyl-substituted C _6-14 aryl groups are most preferred, and perfluoro C _1-3 alkyl-substituted phenyl groups are particularly preferred.

The number of fluoroalkyl groups in the fluoroalkyl-substituted aryl group represented by R ¹² f is, for example, 1 to 5, preferably 1 to 3, particularly preferably 1 or 2.

In formula (a-2), t represents an integer of 1 to 4, preferably an integer of 2 to 4, particularly preferably 3 or 4, most preferably 4.

In formula (a-2), u represents 0 or 1.

Examples of the anion represented by the formula (a-2) include tetrakis[fluorophenyl] such as tetrafluorogallate anion, tetrakis(pentafluorophenyl)gallate anion; tetrakis(4-fluorophenyl)gallate anion, and the like. Gallate anion; tetrakis [difluorophenyl] gallate anion such as tetrakis (3,5-difluorophenyl) gallate anion; tris (pentafluorophenyl) fluorogallate anion, bis (pentafluorophenyl) difluorogallate anion, ( pentafluorophenyl)trifluorogallate anion; tetrakis[(C _1-5 haloalkyl)phenyl]gallate anion such as tetrakis[4-(trifluoromethyl)phenyl]gallate anion; tetrakis[3,5-bis(tri tetrakis[bis(C _1-5 haloalkyl)phenyl]gallate anions such as fluoromethyl)phenyl]gallate anions; tris[(C _1-5 haloalkyl) _phenyl ]fluorogallate anions, etc.; Bis[(C _1-5 haloalkyl)phenyl]difluorogallate anion such as 4-(trifluoromethyl)phenyl]difluorogallate anion; bis[3,5-bis(trifluoromethyl)phenyl]difluorogallate anion etc. bis[bis(C _1-5 haloalkyl)phenyl]difluorodifluorogallate anion; [(C _1-5 haloalkyl)phenyl]trifluorogallate such as [4-(trifluoromethyl)phenyl]trifluorogallate anion Anions; [bis(C _{1-5 haloalkyl)phenyl]trifluorogallate anions such as [3,5-} bis(trifluoromethyl)phenyl]trifluorogallate anions and the like.

When the acid generator contains a salt (1-1) of a cation represented by the above formula (c-1) and an anion represented by the above formula (a-1), Solubility tends to be further improved.

Further, when the acid generator contains a salt (1-2) of a cation represented by the formula (c-1) and an anion represented by the formula (a-2), the acid generator The cured product obtained by using has a tendency to improve heat yellowing resistance.

The acid generator may contain other salt (=compound that generates an acid by thermal decomposition) other than the salt (1). For example, a cation represented by the following formula (c-2), It may contain a salt (2) with an anion represented by the above formula (a-1) or (a-2).

The salt (2) includes a salt (2-1) of a cation represented by the above formula (c-2) and an anion represented by the above formula (a-1), and the above formula (c-2) and a salt (2-2) of the cation represented by and the anion represented by the above formula (a-2).

The acid generator is represented by the above formula (c-2) together with a salt (1-1) of the cation represented by the above formula (c-1) and the anion represented by the above formula (a-1). and a salt (2-1) of the cation represented by the above formula (a-1).

Further, the acid generator is a salt (2-1) of a cation represented by the above formula (c-1) and an anion represented by the above formula (a-2), together with the above formula (c-2). and a salt (2-2) of the cation represented by and the anion represented by the above formula (a-2).

In the above formula (c-2), n represents an integer of 1 or more. R ¹ , R ² and R ³ are the same as above.

n is an integer of 1 or more, for example an integer of 1 to 3, preferably 1 or 2;

When both the salt (1) and the salt (2) are contained in the acid generator, the solubility in the cationic curable compound tends to be improved and/or the thermal yellowing of the obtained cured product tends to be improved.

When the acid generator contains salt (1) and salt (2), the content of salt (1) (or salt (1) in the total 100% by weight of salt (1) and salt (2) ) is, for example, more than 95% by weight and not more than 99.999% by weight. The content of the salt (1) is preferably 96% by weight or more, more preferably 96.5% by weight or more, particularly preferably 97% by weight or more, and 98% by weight, in terms of excellent decomposition efficiency and excellent curability. Above 98.5% by weight is most preferred, and above 98.5% by weight is particularly preferred. In addition, the content of the salt (1) is preferably 99.99% by weight or less, more preferably 99.9% by weight or less, and even more preferably 99.8% by weight or less, from the viewpoint of further improving solubility. , 99.7% by weight or less is particularly preferred, 99.5% by weight or less is most preferred, and 99.3% by weight or less is particularly preferred.

When the acid generator contains salt (1) and salt (2), the content of salt (2) in the total amount of the acid generator (or a total of 100% by weight of salt (1) and salt (2) , the ratio of the salt (2) in) is, for example, 0.001% by weight or more and 5% by weight or less. The lower limit of the content of the salt (2) is preferably 0.005% by weight from the viewpoint of improving the solubility in the cationic curable compound and/or improving the heat yellowing of the obtained cured product. , more preferably 0.01 wt%, more preferably 0.02 wt%, more preferably 0.1 wt%, more preferably 0.2 wt%, particularly preferably 0.3 wt%, 0.5 wt% % is most preferred, and 0.7% by weight is especially preferred. The content of the salt (2) is preferably 4% by weight or less, more preferably 3.5% by weight or less, in terms of excellent decomposition efficiency, excellent curability, and obtaining a cured product with excellent insulation. Preferably, less than 3% by weight is more preferable, 2% by weight or less is particularly preferable, 1.5% by weight or less is most preferable, and 1% by weight or less is particularly preferable.

When the acid generator contains salt (1) and salt (2), the content of salt (1) and salt (2) can be calculated, for example, from the peak area ratio obtained using HPLC. can be done.

The acid generator may further contain other salts in addition to the salt (1) and salt (2). The ratio of the total content of salt (1) and salt (2) is, for example, 80% by weight or more, preferably 90% by weight or more, particularly preferably 95% by weight or more, most preferably 99% by weight or more, and particularly preferably 99.9% by weight or more. The upper limit of the total content is 100% by weight.

The acid generator has excellent solubility in cationic curable compounds, for example, 3',4'-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane carboxylate ( To a mixture of 70 parts by weight of bisphenol A-type diglycidyl ether (trade name "jER828", manufactured by Mitsubishi Chemical Corporation) and 70 parts by weight of bisphenol A-type diglycidyl ether (trade name "JER828" manufactured by Mitsubishi Chemical Corporation), 2 weights of the acid generator was added. parts and stirred with a stirrer tip of 2 cm in length at a stirring speed of 100 rpm, the time required for the acid generator to dissolve completely is, for example, 5 minutes or less, preferably 3 minutes or less, more preferably 3 minutes or less. is less than 2 minutes. The lower limit of the time required for the acid generator to dissolve completely is, for example, 0.1 minute.

When the acid generator contains the salt (1) and the salt (2), the solubility in the cationic curable compound is further improved, compared with the case where the acid generator contains the salt (1) alone. The time required tends to be shortened. The time required for complete dissolution of the acid generator when added to the mixture of cationic curable compounds in the above ratio and stirred under the above conditions is, for example, less than 1 minute, preferably 0.5 minute or less.

Under exactly the same conditions except that the composition of the acid generator is different, the time required for the acid generator to completely dissolve in the cationic curable compound is compared to the case where the acid generator contains salt (1) alone. When the acid generator contains salt (1) and salt (2), it tends to be shortened, and the shortening rate is, for example, 20% or more, preferably 30% or more, and particularly preferably 40% or more. The upper limit of the shortening rate is, for example, 80%.

The acid generator has excellent heat sensitivity, and when subjected to a heat treatment (for example, a treatment of heating at a temperature of 70 to 120° C. for 30 to 120 minutes), it rapidly decomposes to form an acid (H(R ¹¹ f) _s It generates PF _6-s or H([R ¹² f(O) _u ] _t GaF _4-t ).Therefore, the acid generator can be suitably used as a heat-sensitive acid generator.

[Method for producing acid generator]
A method for producing an acid generator containing a salt (1-1) of a cation represented by the formula (c-1) and an anion represented by the formula (a-1), and the salt (1-1) ) and a salt (2-1) of a cation represented by the above formula (c-2) and an anion represented by the above formula (a-1). show. An acid generator containing an anion represented by the formula (a-2) instead of the anion represented by the formula (a-1) can be produced in the same manner.

The salt (1-1) can be produced, for example, through the following steps I and II. Also, the salt (2-1) can be produced, for example, through the following steps I, III, and IV. In the following formula, A represents a halogen atom and M represents an alkali metal (lithium, sodium, potassium, etc.). R ¹ , R ² , R ³ , R ¹¹ f, s and n are the same as above.

An acid generator containing the salt (1-1) can be produced, for example, through the above steps I and II. Further, the salt (1-1) and the acid generator containing the salt (2-1) are produced by, for example, producing the salt (1-1) through the above steps I and II, followed by the above steps I, III, and IV. It can be produced by preparing salt (2-1) and blending the obtained salt (1-1) with the salt (2-1). Furthermore, the reaction of step I and the reaction of step III are allowed to proceed simultaneously to obtain a mixture of the compound represented by the above formula (3) and the compound represented by the above formula (5), and the resulting mixture is subjected to salt exchange. A mixture of salt (1-1) and salt (2-1) may be produced by the reaction.

(Process I)
In step I, a compound represented by formula (1) (=compound (1)) and a compound represented by formula (2) (=compound (2)) are reacted to obtain a compound represented by formula (3). (=Compound (3)).

The molar ratio (compound (1)/compound (2)) of compound (1) and compound (2) subjected to the reaction is, for example, 1/3 to 3/1, preferably 1/2 to 2/1. .

The reaction can be carried out in the presence of a solvent. Examples of the solvent include acetone, acetonitrile, dimethylsulfoxide and the like. These can be used individually by 1 type or in combination of 2 or more types.

The reaction temperature is, for example, 25-50°C.

(Step II)
In step II, compound (3) obtained in step I is reacted with M(R ¹¹ f) _s PF _6-s to perform salt exchange to obtain a compound represented by formula (4) (=salt (1 -1)) is obtained.

The molar ratio of compound (3) and M(R ¹¹ f) _s PF _6-s to be subjected to the reaction (compound (3)/M(R ¹¹ f) _s PF _6-s ) is, for example, 1/3 to 3. /1, preferably 1/2 to 2/1.

The reaction can be carried out in the presence of a solvent. Examples of the solvent include water, ethyl acetate, and dichloromethane. These can be used individually by 1 type or in combination of 2 or more types.

The reaction temperature is, for example, 15 to 35°C.

(Step III)
Step III is a step of reacting compound (3) obtained through step I with compound (2) to obtain a compound represented by formula (5).

The molar ratio of compound (3) to compound (2) (compound (3)/compound (2)) is, for example, 2/1 to 1/3, preferably 1/1 to 1/2.

The reaction can be carried out in the presence of a solvent. Examples of the solvent include acetonitrile, N,N-dimethylformamide, dimethylsulfoxide and the like. These can be used individually by 1 type or in combination of 2 or more types.

The reaction temperature is, for example, 40-70°C.

(Step IV)
In step IV, the compound (5) obtained in step III is reacted with M(R ¹¹ f) _s PF _6-s to perform salt exchange to obtain a compound represented by formula (6) (=salt (2 -1)) is obtained.

The molar ratio of compound (5) and M(R ¹¹ f) _s PF _6-s to be subjected to the reaction (compound (5)/M(R ¹¹ f) _s PF _6-s ) is, for example, 1/3 to 3. /1, preferably 1/2 to 2/1.

The reaction can be carried out in the presence of a solvent. Examples of the solvent include water, ethyl acetate, and dichloromethane. These can be used individually by 1 type or in combination of 2 or more types.

The reaction temperature is, for example, 15 to 35°C.

The atmosphere for the reaction is not particularly limited as long as it does not inhibit the reaction, and may be, for example, an air atmosphere, a nitrogen atmosphere, an argon atmosphere, or the like. Moreover, the reaction can be carried out by any method such as a batch system, a semi-batch system, or a continuous system.

After completion of the reaction in each step, the obtained reaction product may be subjected to general separation and purification treatments (eg, precipitation, washing, filtration, etc.).

[Curable composition]
The curable composition of the present invention contains the acid generator and a cationic curable compound. Each of the acid generator and the cationic curable compound may be contained singly or in combination of two or more.

The content of the acid generator is, for example, 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the cationic curable compound.

The cationic curable compound is a compound having one or more cationic curable groups selected from epoxy groups, oxetanyl groups, vinyl ether groups and the like. The epoxy group is a group containing a 3-membered cyclic ether skeleton, and the oxetanyl group is a group containing a 4-membered cyclic ether skeleton.

The number of cationic curable groups in one molecule of the cationic curable compound is 1 or more, preferably 1 to 4 groups, more preferably 2 to 4 groups, and particularly preferably 2 to 4 groups in terms of excellent solubility of the acid generator. is 2-3.

Molecular weight per cationically curable group of the cationically curable compound (e.g., cationically curable group equivalent such as epoxy equivalent and oxetane equivalent) is, for example, 50 to 500 g/eq, preferably 100 to 400 g/eq, more preferably is between 100 and 300 g/eq.

Examples of the cationically curable compound include compounds having an epoxy group as a cationically curable group (=epoxy compound), compounds having an oxetanyl group as a cationically curable group (=oxetane compound), and vinyl ether groups as a cationically curable group. compounds (= vinyl ether compounds), compounds having an epoxy group and an oxetanyl group as cationically curable groups, compounds having an epoxy group and a vinyl ether group as cationically curable groups, compounds having an oxetanyl group and a vinyl ether group as cationically curable groups, etc. is mentioned.

(epoxy compound)
Epoxy compounds include, for example, epoxy-modified siloxane compounds, alicyclic epoxy compounds (alicyclic epoxy resins), aromatic epoxy compounds (aromatic epoxy resins), aliphatic epoxy compounds (aliphatic epoxy resins), and the like. .

<Epoxy-modified siloxane compound>
Examples of the epoxy-modified siloxane compound include epoxy-modified silicone and epoxy-modified polyorganosilsesquioxane.

<Alicyclic epoxy compound>
Examples of the alicyclic epoxy compound include known or commonly used compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, and are not particularly limited. Examples include the following compounds. be done.
(1) A compound having an alicyclic epoxy group (=an epoxy group composed of two adjacent carbon atoms forming an alicyclic ring and an oxygen atom in the molecule) (2) A compound having an alicyclic ring and a glycidyl ether group

Examples of the compound (1) having an alicyclic epoxy group include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy- 1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy- 3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3, 4-epoxy)cyclohexane metadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene bis(3,4-epoxycyclohexanecarboxylate) and the like.

Examples of the compound (2) having an alicyclic ring and a glycidyl ether group include glycidyl ethers of alicyclic alcohols (in particular, alicyclic polyhydric alcohols). More specifically, for example, 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane, 2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy) Compounds obtained by hydrogenating bisphenol A type epoxy compounds such as cyclohexyl]propane (hydrogenated bisphenol A type epoxy compounds); bis[o,o-(2,3-epoxypropoxy)cyclohexyl]methane, bis[o , p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[p,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[3,5-dimethyl-4-(2, Compounds obtained by hydrogenating bisphenol F type epoxy compounds such as 3-epoxypropoxy)cyclohexyl]methane (hydrogenated bisphenol F type epoxy compounds); hydrogenated biphenol type epoxy compounds; hydrogenated phenol novolac type epoxy compounds; hydrogenated cresol Hydrogenated cresol novolak type epoxy compounds of bisphenol A; hydrogenated naphthalene type epoxy compounds; and hydrogenated trisphenolmethane type epoxy compounds.

<Aromatic epoxy compound>
Examples of the aromatic epoxy compounds include epibis-type glycidyl ether type epoxy resins obtained by a condensation reaction between bisphenols [eg, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc.] and epihalohydrin; High-molecular-weight epibis-type glycidyl ether-type epoxy resin obtained by subjecting a bis-type glycidyl ether-type epoxy resin to further addition reaction with the above bisphenols; F, bisphenol S, etc.] and aldehydes [e.g., formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, etc.] and polyhydric alcohols obtained by condensation reaction with epihalohydrin. Alkyl-type glycidyl ether type epoxy resin; two phenol skeletons are bonded to the 9-position of the fluorene ring, and the oxygen atoms obtained by removing the hydrogen atoms from the hydroxy groups of these phenol skeletons are directly or via alkyleneoxy groups, respectively, glycidyl Epoxy compounds to which groups are bonded and the like can be mentioned.

<Aliphatic epoxy compound>
Examples of the aliphatic epoxy compounds include glycidyl ethers of q-valent alcohols having no cyclic structure (where q is a natural number); monovalent or polyvalent carboxylic acids [e.g. adipic acid, sebacic acid, maleic acid, itaconic acid, etc.]; epoxidized oils and fats having double bonds such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; polyolefins (poly (including alkadienes) epoxidized products, and the like. Examples of alcohols having no q-valent cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, and 1-butanol; ethylene glycol, 1,2-propanediol, 1 Dihydric alcohols such as ,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol; trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol; The q-valent alcohol may also be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or the like.

(oxetane compound)
Examples of the oxetane compounds include 3,3-bis(vinyloxymethyl)oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3 -(hydroxymethyl)oxetane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane, 3,3- bis(chloromethyl)oxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, bis([1-ethyl(3-oxetanyl)]methyl)ether, 4,4'-bis[ (3-ethyl-3-oxetanyl)methoxymethyl]bicyclohexyl, 4,4′-bis[3-ethyl-(3-oxetanyl)methoxymethyl]biphenyl, 1,4-bis[(3-ethyl-3-oxetanyl) ) methoxymethyl]cyclohexane, 1,4-bis([(3-ethyl-3-oxetanyl)methoxy]methyl)benzene, 3-ethyl-3([(3-ethyloxetan-3-yl)methoxy]methyl)oxetane , xylylene bisoxetane, and the like.

(vinyl ether compound)
Examples of the vinyl ether compound include aryl vinyl ethers such as phenyl vinyl ether; alkyl vinyl ethers such as n-butyl vinyl ether and n-octyl vinyl ether; cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 2-hydroxy vinyl ethers having a hydroxyl group such as butyl vinyl ether; and many vinyl ethers such as hydroquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexanedivinyl ether, cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether. Examples include functional vinyl ethers.

As the cationic curable compound, an alicyclic epoxy compound having one or more (preferably 1 to 4) alicyclic epoxy groups (in particular, having 2 or more (preferably 2 to 4) alicyclic epoxy groups It is preferable to contain at least a polyfunctional alicyclic epoxy compound).

The cationic curable compound includes the alicyclic epoxy compound, a glycidyl ether type epoxy compound having one or more (preferably 1 to 4) glycidyl ether groups and/or one or more oxetanyl groups (preferably 1 to 4) may be used in combination. When used in combination, the mixing ratio [alicyclic epoxy compound/(glycidyl ether type epoxy compound and oxetane compound); weight ratio] is, for example, 95/5 to 5/95, preferably 95/5 to 30/70, More preferably 95/5 to 40/60, still more preferably 95/5 to 60/40, particularly preferably 90/10 to 65/35, most preferably 85/15 to 65/35.

The curable composition may optionally contain one or more components other than the components described above. Other components include, for example, sensitizers, sensitizing aids, antioxidants, stabilizers, surfactants, solvents, rheology control agents, leveling agents, silane coupling agents, fillers, conductive particles, Polymerization inhibitors, light stabilizers, plasticizers, antifoaming agents, foaming agents, UV absorbers, tackifiers, curing retarders, ion adsorbents, pigments, dyes, phosphors, release agents, antistatic agents, flame Fire retardants, radical curable compounds, polyimide resins, polyamide resins, phenoxy resins, poly(meth)acrylate resins, polyurethane resins, polyurea resins, polyester resins, polyvinyl butyral resins, SBS, SEBS and the like can be mentioned. The content of these (the total amount when two or more are contained) is, for example, 50% by weight or less, preferably 10% by weight or less, and particularly preferably 5% by weight or less of the total amount (100% by weight) of the curable composition. be. The content of these is, for example, 0.05% by weight or more, preferably 0.1% by weight or more, based on the total amount (100% by weight) of the curable composition.

The curable composition is prepared by mixing the acid generator, the cationically curable compound, and other optional components in a rotary-revolution stirring and defoaming device, a homogenizer, a planetary mixer, a three-roll mill, a bead mill, or the like. It can be produced by uniformly mixing using a generally known mixing device. In addition, each component may be mixed simultaneously and may be mixed one by one.

The acid generator contained in the curable composition has excellent solubility in the cationic curable compound, and can be reliably dissolved by a short-time dissolving operation. In addition, precipitation over time can also be suppressed. Therefore, the curable composition can be efficiently prepared, and after preparation, there is plenty of time before use, and it is easy to handle.

Since the curable composition contains the acid generator in a completely dissolved state, it has excellent curability. do not have. In addition, the cured product is excellent in heat resistance to yellowing, and can stably maintain transparency even when exposed to a high temperature environment.

Applications of the curable composition are not particularly limited. Examples include impregnating agents, fillers, sealants, encapsulants, and materials for stereolithography.

Since the curable composition can form a cured product having excellent resistance to heat yellowing as described above, it can be suitably used as a raw material for optical materials. The optical materials include lenses such as spectacle lenses, (digital) camera imaging lenses, light beam condensing lenses, and light diffusion lenses; LED sealing materials, optical adhesives, optical transmission bonding materials, Prisms, filters, diffraction gratings, cover glasses for display devices, etc. are included.

[Cured product]
The cured product of the present invention is a cured product of the curable composition.

The cured product is obtained by curing the curable composition.

The curable composition can be cured by heat treatment. The heating temperature is, for example, 70-120.degree. The heating time is, for example, 0.5 to 2 hours.

In the cured product, the insoluble matter of the acid generator does not remain or the residual amount of the insoluble matter of the acid generator is extremely low. More specifically, the electrical conductivity of the extracted water obtained by the method described in the Examples) is, for example, less than 50 μS/cm, preferably 40 μS/cm or less, particularly preferably 30 μS/cm or less, and most preferably 25 μS/cm. cm.

The cured product has low electrical conductivity and excellent insulating properties as described above. Therefore, if the cured product is used for encapsulation, a semiconductor device having excellent short-circuit prevention properties and high reliability can be obtained.

In addition, when the acid generator is unevenly distributed in the cured product, the acid generator decomposes and non-uniformly generates acid when exposed to a high temperature environment, causing yellowing of the cured product. However, since the cured product uniformly contains the acid generator or uneven distribution of the acid generator is suppressed, yellowing due to acid is suppressed even when exposed to a high temperature environment, and the hue of the cured product is stabilized. can be held.

The cured product is inhibited from yellowing due to high temperature exposure, and the rate of increase in yellowness (YI) calculated from the following formula is, for example, 130% or less, preferably 120% or less, more preferably 110% or less, and still more preferably is 90% or less, more preferably 80% or less, more preferably 70% or less, particularly preferably 50% or less, most preferably 25% or less, particularly preferably 10% or less. The lower limit of the rate of increase in yellowness index (YI) is 0%.
Yellowness increase rate (%) = [(YIa-YIb) / YIb] × 100
(In the above formula, YIb indicates the yellowness of the cured product before high temperature exposure, and YIa indicates the yellowness of the cured product after high temperature exposure. The high temperature exposure is based on the reflow temperature profile (maximum temperature : 270 ° C)) by conducting a heat resistance test three times in a row)

Further, the yellowness index (YI) of the cured product after exposure to high temperature is, for example, 3.0 or less, preferably 2.5 or less, particularly preferably 2.0 or less, most preferably 1.2 or less, particularly preferably 1 .0 or less. Incidentally, the lower limit of the yellowness index (YI) is 0, for example.

As described above, each configuration and combination thereof of the present invention is an example, and addition, omission, substitution, and modification of configuration are possible as appropriate without departing from the gist of the present invention.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

Example 1
[Preparation of salt (1-1a)]
(Process I)
50.0 g of N,N-dimethylaniline, 64.6 g of 4-methoxybenzyl chloride and 16.9 g of acetonitrile were mixed and heated to 50°C. The temperature of the reaction solution (50° C.) was maintained for 5 hours to complete the reaction.
250 g of acetone was added to the reaction solution, the temperature was lowered to 10° C. or lower, and the mixture was stirred for 1 hour. Thereafter, the reaction solution was subjected to a filtration treatment, and the resulting solid was collected to obtain 81.3 g of N-(4-methoxybenzyl)-N,N-dimethylanilinium chloride.

(Step II)
50.0 g of N-(4-methoxybenzyl)-N,N-dimethylanilinium chloride obtained in step I was dissolved in 200 g of ion-exchanged water, and 250 g of dichloromethane and potassium tris(perfluoroethyl)trifluorophosphate 26 were added. .4 g were charged sequentially.
After the addition was completed, the mixture was stirred at room temperature for 1 hour to complete the reaction, the aqueous layer was removed, and the organic layer was washed with 300 g of ion-exchanged water three times. After that, the organic layer is desolvated, and a salt of a cation represented by the following formula (c-1-1) and a tris(perfluoroethyl)trifluorophosphate anion ((CF ₃ CF ₂ ) ₃ PF ₃ ⁻ ) ( 1-1a) 113 g was obtained. ¹ H-NMR of the obtained salt (1-1a) is shown in FIG. 1, and ¹⁹ F-NMR measurement results are shown in FIG.
The resulting salt (1-1a) was used as acid generator 1.

Example 2
[Preparation of salt (1-1a)]
In ^the same _manner as _in Example 1, a salt _{( 1} -1a).

[Preparation of salt (2-1a)]
(Process I)
N-(4-methoxybenzyl)-N,N-dimethylanilinium chloride was obtained in the same manner as in Step I of Example 1.

(Step III)
10 g of the obtained N-(4-methoxybenzyl)-N,N-dimethylanilinium chloride was dissolved in 5.31 g of acetonitrile, and 8.45 g of 4-methoxybenzyl chloride was added.
After the addition, the temperature was raised to 70° C. and the mixture was stirred for 5 hours to complete the reaction.
After adding 30 g of ion-exchanged water and 50 g of ethyl acetate to the reaction solution and stirring at room temperature for 30 minutes, the aqueous layer was removed, and the organic layer was washed three times with 30 g of ion-exchanged water to remove the solvent.
After removal of the solvent, 5.0 g of methanol was added to the obtained yellow oily residue to dissolve it, thereby obtaining a methanol solution. The resulting methanol solution was slowly added to 30.0 g of stirred methyl-tert-butyl ether to precipitate crystals.
The precipitated crystals were separated by filtration and dried under reduced pressure to obtain 9.48 g of a chloride salt of a cation represented by the following formula (c-2-1) (where n1=1).

(Step IV)
7.95 g of the resulting chloride salt is salt-exchanged with 9.65 g of potassium tris(perfluoroethyl)trifluorophosphate in the same manner as in Step II of Example 1 to give the above formula (c-2-1). 13.8 g of a salt (2-1a) of the represented cation (n1=1 in the formula) and tris(perfluoroethyl)trifluorophosphate anion ((CF ₃ CF ₂ ) ₃ PF ₃ ⁻ ) was obtained.

[Preparation of acid generator]
99.98 g of the obtained salt (1-1a) and 0.02 g of the salt (2-1a) were mixed to obtain an acid generator having a salt (2-1a) content of 0.02% by weight based on the total amount of the mixture. got 2.

Example 3
Acid generator 3 was obtained in the same manner as in Example 2, except that the content of salt (2-1a) was changed to 0.1% by weight in the [Preparation of acid generator] step.

Example 4
Acid generator 4 was obtained in the same manner as in Example 2, except that the content of salt (2-1a) was changed to 0.5% by weight in the [Preparation of acid generator] step.

Example 5
Acid generator 5 was obtained in the same manner as in Example 2, except that the content of salt (2-1a) was changed to 1% by weight in the [Preparation of acid generator] step.

Example 6
Acid generator 6 was obtained in the same manner as in Example 2, except that the content of salt (2-1a) was changed to 3% by weight in the [Preparation of acid generator] step.

Example 7
Acid generator 7 was obtained in the same manner as in Example 2, except that the content of salt (2-1a) was changed to 5% by weight in the [Preparation of acid generator] step.

Comparative example 1
Acid generator 10 was a salt of B(C ₆ F ₅ ) ₄ ⁻ with the cation represented by the above formula (c-1-1).

Comparative example 2
A salt of the cation represented by the above formula (c-1-1) and SbF ₆ ⁻ was obtained and used as acid generator 11.

Comparative example 3
A salt of the cation represented by the above formula (c-1-1) and PF ₆ ⁻ was obtained and used as acid generator 12 .

Examples 8-20, Comparative Examples 4-6
(Preparation of curable composition)
A beaker was charged with each component according to the formulation shown in the table below (unit: parts by weight), and a stirrer was added to perform dissolution treatment by stirring at 20° C. and 100 rpm to obtain a curable composition.

Example 21
[Preparation of salt (1-2a)]
A cation represented by the above formula (c-1-1) was prepared in the same manner as in Example 1 except that sodium tetrakis(pentafluorophenyl)gallate was used instead of potassium tris(perfluoroethyl)trifluorophosphate. and a salt (1-2a) of tetrakis(pentafluorophenyl)gallate anion (Ga(C ₆ F ₅ ) ₄ ⁻ ). ¹ H-NMR of the obtained salt (1-2a) is shown in FIG. 3, and ¹⁹ F-NMR measurement results are shown in FIG.
The resulting salt (1-2a) was used as acid generator 8.

Example 22
[Preparation of salt (1-2a)]
A salt (1-2a) of the cation represented by the above formula (c-1-1) and tetrakis(pentafluorophenyl)gallate anion (Ga(C ₆ F ₅ ) ₄ ⁻ ) was prepared in the same manner as in Example 21. ).

[Preparation of salt (2-2a)]
In the same manner as in the preparation of salt (2-1a) of Example 2, except that sodium tetrakis(pentafluorophenyl)gallate was used instead of potassium tris(perfluoroethyl)trifluorophosphate, the above formula (c- A salt (2-2a) of a cation represented by 2-1) (n1=1 in the formula) and a tetrakis(pentafluorophenyl)gallate anion (Ga(C ₆ F ₅ ) ₄ ⁻ ) was obtained.

[Preparation of acid generator]
99.98 g of the obtained salt (1-2a) and 0.02 g of the salt (2-2a) were mixed to obtain an acid generator having a salt (2-2a) content of 0.02% by weight based on the total amount of the mixture. got 9.

Examples 23-25
(Preparation of curable composition)
A beaker was charged with each component according to the formulation shown in the table below (unit: parts by weight), and a stirrer was added to perform dissolution treatment by stirring at 20° C. and 100 rpm to obtain a curable composition.

(Solubility evaluation)
In Examples 8 to 20, 23 to 25, and Comparative Examples 4 to 6, the dissolution treatment time required for the acid generator to dissolve completely was measured, and the solubility was evaluated according to the following criteria.
<Evaluation Criteria>
◎ (excellent): dissolution treatment time is less than 1 minute ○ (good): dissolution treatment time is 1 minute or more and 5 minutes or less × (improper): dissolution treatment time is more than 5 minutes

Reference examples 1 and 2
A beaker was charged with each component according to the formulation shown in the table below (unit: parts by weight), and the mixture was stirred at 20° C. and 100 rpm for 0.5 minutes with a stirrer to obtain a curable composition.
Insoluble matter remained in the resulting curable composition.

(Curability evaluation)
The curable compositions obtained in Examples, Comparative Examples, and Reference Examples were coated on a polyphenylene ether substrate using a bar coater to a thickness of 50 μm. After that, heat treatment was performed for 1 hour in a hot air dryer at 100° C. to obtain a cured product.
The surface of the obtained cured product was rubbed with a cotton swab impregnated with acetone under a load of 300 g or 500 g 10 times, and the rubbed surface was visually observed to evaluate the curability according to the following criteria.
<Evaluation Criteria>
◎ (Excellent): No change in appearance when rubbed with a load of 500 g ○ (Good): Killing was confirmed when rubbed with a load of 500 g, but no change in appearance when rubbed with a load of 300 g △ (Fair) ): When rubbed with a load of 300 g, no loss of luster or dissolution of the film was confirmed, but scratches were confirmed. confirmed

(insulation evaluation)
For the curable compositions obtained in Examples, Comparative Examples, and Reference Examples, the curable compositions were obtained in the same manner as in the above (Evaluation of curability), and the obtained cured products were peeled off from the polyphenylene ether substrate. About 0.2 g was precisely weighed and used as a test piece.
A Teflon (registered trademark) PCT container containing the test piece thus obtained and 10 g of ion-exchanged distilled water was placed in a SUS pressure vessel and sealed. After standing for hours, it was allowed to cool to room temperature.
After that, the moisture in the PCT container was taken out, the conductivity was measured, and the insulation was evaluated according to the following criteria.
<Evaluation Criteria>
◎ (excellent): conductivity is less than 25 μS / cm ○ (good): conductivity is 25 μS / cm or more and less than 50 μS / cm △ (acceptable): conductivity is 50 μS / cm or more and less than 100 μS / cm × (improper): conductivity rate is 100 μS/cm or more

(Heat-resistant yellowing evaluation)
A spacer of 20 mm length×20 mm width×0.1 mm thickness was prepared and sandwiched between slide glasses.
The spacer is filled with the curable compositions obtained in Examples, Comparative Examples, and Reference Examples, and then heat-treated at 130 ° C. for 1 hour using a hot air dryer to obtain the curable composition. The product was cured to obtain a cured product. The yellowness index (YIb) of the obtained cured product was measured.
After that, the obtained cured product was subjected to a heat resistance test based on the reflow temperature profile (maximum temperature: 270 ° C.) described in the JEDEC standard three times in succession, and the yellowness (YIa) of the cured product after the heat resistance test was measured. bottom. YIb and YIa were measured with a spectrophotometer using a D65 light source. Then, the increase rate (%) of YI was calculated from the following formula.
Rate of increase in YI (%) = [(YIa-YIb)/YIb] x 100

ＯＸＴ－１２１：１，４－ビス［（３－エチルオキセタン－３－イル）メトキシメチル］ベンゼン、オキセタン当量１６７ｇ／ｅｑ、１分子中のオキセタニル基数２、東亜合成（株）製
ＯＸＴ－２２１：３，３’－（オキシビスメチレン）ビス（３－エチルオキセタン）、東亜合成（株）製
ＥＸ－１４６：ｐ－ｔｅｒｔ－ブチルフェニルグリシジルエーテル、オキセタン当量１０７ｇ／ｅｑ、１分子中のオキセタニル基数２、商品名「デナコールＥＸ－１４６」、ナガセケムテックス（株）製
＜シランカップリング剤＞
ＫＢＭ－４０３：３－グリシドキシプロピルトリメトキシシラン、信越化学工業（株）製
＜消泡剤＞
ＢＹＫ１７９０：ビックケミー・ジャパン（株）製
＜レベリング剤＞
ＬＳ－４６０：エーテル変性シリコーン、楠本化成（株）製 <Cationic curable compound>
2021P: 3′,4′-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane carboxylate, epoxy equivalent 127 g/eq, number of epoxy groups per molecule 2, trade name “Celoxide 2021P”, manufactured by Daicel Corporation jER828 : Bisphenol A diglycidyl ether, epoxy equivalent 189 g/eq, number of epoxy groups per molecule 2, manufactured by Mitsubishi Chemical Corporation jERYX8000: Hydrogenated bisphenol A diglycidyl ether, epoxy equivalent 205 g/eq, Mitsubishi Chemical Corporation VG3101L manufactured by Printec Co., Ltd.: epoxy compound represented by the following formula, epoxy equivalent 209 g/eq, number of epoxy groups per molecule 3, trade name "TECHMORE VG3101L", manufactured by Printec Co., Ltd.

OXT-121: 1,4-bis[(3-ethyloxetan-3-yl)methoxymethyl]benzene, oxetane equivalent 167 g/eq, number of oxetanyl groups per molecule 2, manufactured by Toagosei Co., Ltd. OXT-221:3 , 3′-(oxybismethylene)bis(3-ethyloxetane), EX-146 manufactured by Toagosei Co., Ltd.: p-tert-butylphenyl glycidyl ether, oxetane equivalent 107 g/eq, number of oxetanyl groups per molecule 2, Product name “Denacol EX-146”, manufactured by Nagase ChemteX Co., Ltd. <Silane coupling agent>
KBM-403: 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. <Antifoaming agent>
BYK1790: BYK-Chemie Japan Co., Ltd. <leveling agent>
LS-460: Ether-modified silicone, manufactured by Kusumoto Kasei Co., Ltd.

Claims (4)

An acid generator containing a salt (1) of a cation represented by the following formula (c-1) and an anion represented by the following formula (a-1) or (a-2).

(In formula (c-1), R ¹ , R ² and R ³ are the same or different and represent an alkyl group having 1 to 6 carbon atoms. In formula (a-1), R ¹¹ f represents a fluoroalkyl group. , s represents an integer of 1 to 5. In formula (a-2), R ¹² f represents a fluoroalkyl group, a fluoroaryl group, or a fluoroalkyl-substituted aryl group, and t represents an integer of 1 to 4. and u indicates 0 or 1) Further, a salt (2) of a cation represented by the following formula (c-2) and the anion is included, and the content of the salt (2) is 0.001% by weight or more and 5% by weight or less. 2. The acid generator according to 1.

(In formula (c-2), n represents an integer of 1 or more. R ¹ , R ² and R ³ are the same as above.) A curable composition comprising the acid generator according to claim 1 or 2 and a cationic curable compound. A cured product of the curable composition according to claim 3 .

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