CATIONIC CURING AGENT, METHOD FOR PRODUCING SAME AND CATIONICALLY CURABLE COMPOSITION

Abstract

A cationic curing agent includes porous particles and a compound represented by General Formula (1), where the compound is held in the porous particles.

##STR00001##

In the General Formula (1), R.sup.1 is an alkyl group having 1 to 18 carbon atoms or a phenyl group, where the alkyl group may be branched and the alkyl group and the phenyl group may each further have a substituent. R.sup.2 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms where the alkyl group may be branched, a halogenoalkyl group, an alkoxy group, or a phenoxy group; where the alkyl group, the halogenoalkyl group, the alkoxy group, or the phenoxy group may further have a substituent. R.sup.1 and R.sup.2 may be identical to or different from each other.

Claims

1: A cationic curing agent, comprising: porous particles; and a compound represented by General Formula (1) below, the compound being held in the porous particles: ##STR00021## where, in the General Formula (1), R.sup.1 is an alkyl group having 1 to 18 carbon atoms or a phenyl group, where the alkyl group may be branched and the alkyl group and the phenyl group may each further have a substituent, R.sup.2 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms where the alkyl group may be branched, a halogenoalkyl group, an alkoxy group, or a phenoxy group, where the alkyl group, the halogenoalkyl group, the alkoxy group, or the phenoxy group may further have a substituent, and R.sup.1 and R.sup.2 may be identical to or different from each other.

2: A cationic curing agent, comprising: porous particles; and a mixture of a compound represented by General Formula (1) below and a compound represented by General Formula (2) below, the mixture being held in the porous particles: ##STR00022## where, in the General Formula (1), R.sup.1 is an alkyl group having 1 to 18 carbon atoms or a phenyl group, where the alkyl group may be branched and the alkyl group and the phenyl group may each further have a substituent, R.sup.2 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms where the alkyl group may be branched, a halogenoalkyl group, an alkoxy group, or a phenoxy group, where the alkyl group, the halogenoalkyl group, the alkoxy group, or the phenoxy group may further have a substituent, and R.sup.1 and R.sup.2 may be identical to or different from each other, ##STR00023## where, in the General Formula (2), Z represents a hydrogen atom or an electron attractive group, and a is an integer of 0 to 5.

3. The cationic curing agent according to claim 1, wherein the porous particles are organic porous particles or inorganic porous particles.

4: The cationic curing agent according to claim 3, wherein a material of the organic porous particles includes a polyurea resin.

5: The cationic curing agent according to claim 4, wherein the material of the organic porous particles further includes a vinyl resin.

6: The cationic curing agent according to claim 1, wherein surfaces of the porous particles include a reaction product of a silane treatment agent.

7: A method for producing a cationic curing agent, the method comprising; allowing a compound represented by General Formula (1) below and porous particles to coexist in an organic solvent and then removing the organic solvent to hold the compound represented by General Formula (1) in the porous particles: ##STR00024## where, in the General Formula (1), R.sup.1 is an alkyl group having 1 to 18 carbon atoms or a phenyl group, where the alkyl group may be branched and the alkyl group and the phenyl group may each further have a substituent, R.sup.2 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms where the alkyl group may be branched, a halogenoalkyl group, an alkoxy group, or a phenoxy group, where the alkyl group, the halogenoalkyl group, the alkoxy group, or the phenoxy group may further have a substituent, and R.sup.1 and R.sup.2 may be identical to or different from each other.

8: A method for producing a cationic curing agent, the method comprising; allowing a compound represented by General Formula (1) below, a compound represented by General Formula (2) below, and porous particles to coexist in an organic solvent and then removing the organic solvent to hold a mixture of the compound represented by General Formula (1) and the compound represented by General Formula (2) in the porous particles: ##STR00025## where, in the General Formula (1), R.sup.1 is an alkyl group having 1 to 18 carbon atoms or a phenyl group, where the alkyl group may be branched and the alkyl group and the phenyl group may each further have a substituent, R.sup.2 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms where the alkyl group may be branched, a halogenoalkyl group, an alkoxy group, or a phenoxy group, where the alkyl group, the halogenoalkyl group, the alkoxy group, or the phenoxy group may further have a substituent, and R.sup.1 and R.sup.2 may be identical to or different from each other, ##STR00026## where, in the General Formula (2), Z represents a hydrogen atom or an electron attractive group, and a is an integer of 0 to 5.

9: A cationically curable composition, comprising: a cationic curing component; and the cationic curing agent according to claim 1.

10: The cationically curable composition according to claim 9, further comprising an organic silane compound.

11: The cationically curable composition according to claim 10, wherein the organic silane compound is a compound represented by General Formula (2) below: ##STR00027## where, in the General Formula (2), Z represents a hydrogen atom or an electron attractive group, and a is an integer of 0 to 5.

12: The cationic curing agent according to claim 2, wherein the porous particles are organic porous particles or inorganic porous particles.

13: The cationic curing agent according to claim 12, wherein a material of the organic porous particles includes a polyurea resin.

14: The cationic curing agent according to claim 13, wherein the material of the organic porous particles further includes a vinyl resin.

15: The cationic curing agent according to claim 2, wherein surfaces of the porous particles include a reaction product of a silane treatment agent.

16: A cationically curable composition, comprising: a cationic curing component; and the cationic curing agent according to claim 2.

17: The cationically curable composition according to claim 16, further comprising an organic silane compound.

18: The cationically curable composition according to claim 17, wherein the organic silane compound is a compound represented by General Formula (2) below: ##STR00028## where, in the General Formula (2), Z represents a hydrogen atom or an electron attractive group, and a is an integer of 0 to 5.

Description

EXAMPLES

[0162] The present invention will be described below by way of Examples. The present invention, however, shall not be construed as being limited to the Examples.

Synthesis Example 1

[0163] In a state where N.sub.2 was introduced into a 200 mL three-necked flask equipped with a stirrer, a thermometer, and a nitrogen-introducing tube, 5.0 g (20.3 mmol) of aluminum-sec-butoxide (obtained from TOKYO CHEMICAL INDUSTRY Co., Ltd.) and 70 g of heptane were charged into the flask. While the mixture was being stirred at room temperature, 10.79 g (65.0 mmol) of ethyl salicylate (obtained from TOKYO CHEMICAL INDUSTRY Co., Ltd.) was charged thereinto, followed by heating to 100° C. to perform reaction for 2 hours. Crystals started to precipitate immediately after the reaction.

[0164] After completion of the reaction, the reaction mixture was filtrated under reduced pressure to recover the crystals. The crystals were washed with heptane, followed by drying at room temperature under reduced pressure for 24 hours, to obtain 9.75 g of Compound 1 of the following structural formula, as pale red crystals.

##STR00017##

Synthesis Example 2

[0165] In the same manner as in Synthesis Example 1 except that the ethyl salicylate was changed to 11.71 g of n-propyl salicylate (obtained from TOKYO CHEMICAL INDUSTRY Co., Ltd.), 8.82 g of Compound 2 of the following structural formula was obtained as pale red crystals.

##STR00018##

Synthesis Example 3

[0166] In the same manner as in Synthesis Example 1 except that the ethyl salicylate was changed to 12.62 g of n-butyl salicylate (obtained from TOKYO CHEMICAL INDUSTRY Co., Ltd.), 10.10 g of Compound 3 of the following structural formula was obtained as pale red crystals.

##STR00019##

Synthesis Example 4

[0167] In the same manner as in Synthesis Example 1 except that the ethyl salicylate was changed to 10.79 g of methyl 5-methylsalicylate (obtained from TOKYO CHEMICAL INDUSTRY Co., Ltd.), 8.53 g of Compound 4 of the following structural formula was obtained as pale red crystals.

##STR00020##

(Production Example 1 of Porous Particles)

[0168] 800 parts by mass of distilled water, 0.05 parts by mass of a surfactant (NEWREX R-T, obtained from NOF CORPORATION), and 4 parts by mass of polyvinyl alcohol as a dispersant (PVA-205, obtained from KURARAY CO., LTD.) were added to a 3 L-interfacial polymerization container equipped with a thermometer, followed by homogeneously mixing. To the mixture was further added an oil phase solution, which had been prepared by dissolving the following in parts by mass of ethyl acetate: 11 parts by mass of a 24% by mass isopropanol solution of aluminum monoacetylacetonate bis(ethyl acetoacetate) (Aluminum Chelate D, obtained from Kawaken Fine Chemicals Co., Ltd.); and 11 parts by mass of trimethylolpropane (1 mol) adduct of methylenediphenyl-4,4′-diisocyanate (3 mol) (D-109, obtained from MITSUI TAKEDA CHEMICALS, INC.). The resultant mixture was mixed for emulsification with a homogenizer (11,000 rpm/10 min), followed by interfacial polymerization at 60° C. overnight.

[0169] After completion of reaction, the polymerization reaction liquid was left to stand for cooling to room temperature. The interfacial-polymerized particles were separated through filtration and dried at room temperature under reduced pressure for 24 hours, to obtain spherical particles having an average particle diameter of 10.0 μm.

[0170] Moreover, the above particles were washed with methyl ethyl ketone, followed by filtration under reduced pressure, to obtain a wet cake of porous particles A.

(Production Example 2 of Porous Particles)

[0171] 800 parts by mass of distilled water, 0.05 parts by mass of a surfactant (NEWREX R-T, obtained from NOF CORPORATION), and 4 parts by mass of polyvinyl alcohol as a dispersant (PVA-205, obtained from KURARAY CO., LTD.) were added to a 3 L-interfacial polymerization container equipped with a thermometer, followed by homogeneously mixing, to prepare an aqueous phase.

[0172] To the aqueous phase was further added an oil phase, which had been prepared by dissolving the following in 100 parts by mass of ethyl acetate: 100 parts by mass of a 24% by mass isopropanol solution of aluminum monoacetylacetonate bis(ethyl acetoacetate) (Aluminum Chelate D, obtained from Kawaken Fine Chemicals Co., Ltd.); 70 parts by mass of trimethylolpropane (1 mol) adduct of methylenediphenyl-4,4′-diisocyanate (3 mol) as a polyfunctional isocyanate compound (D-109, obtained from MITSUI TAKEDA CHEMICALS, INC.); 30 parts by mass of divinylbenzene as a radical polymerizable compound (obtained from Merck Co., Ltd.); and a radical polymerization initiator (PEROYL L, obtained from NOF CORPORATION) in an amount (0.3 parts by mass) corresponding to 1% by mass of the radical polymerizable compound. The resultant mixture was mixed for emulsification with a homogenizer (10,000 rpm/5 min, T-50, obtained from IKA Japan, K.K.), followed by interfacial polymerization and radical polymerization at 80° C. for 6 hours. After completion of reaction, the polymerization reaction liquid was left to stand for cooling to room temperature. The polymerized particles were separated through filtration and dried at room temperature under reduced pressure for 24 hours, to obtain spherical particles having an average particle diameter of 2.9 μm.

[0173] Moreover, the above particles were washed with methyl ethyl ketone, followed by filtration under reduced pressure, to obtain a wet cake of porous particles B.

(Production Example 3 of Porous Particles)

[0174] 800 parts by mass of distilled water, 0.05 parts by mass of a surfactant (NEWREX R-T, obtained from NOF CORPORATION), and 4 parts by mass of polyvinyl alcohol as a dispersant (PVA-205, obtained from KURARAY CO., LTD.) were added to a 3 L-interfacial polymerization container equipped with a thermometer, followed by homogeneously mixing, to prepare an aqueous phase.

[0175] To the aqueous phase was further added an oil phase, which had been prepared by dissolving the following in 100 parts by mass of ethyl acetate: 100 parts by mass of a 24% by mass isopropanol solution of aluminum monoacetylacetonate bis(ethyl acetoacetate) (Aluminum Chelate D, obtained from Kawaken Fine Chemicals Co., Ltd.); 70 parts by mass of trimethylolpropane (1 mol) adduct of methylenediphenyl-4,4′-diisocyanate (3 mol) as a polyfunctional isocyanate compound (D-109, obtained from MITSUI TAKEDA CHEMICALS, INC.); 30 parts by mass of 1,6-hexanediol diacrylate as a radical polymerizable compound; and a radical polymerization initiator (PEROYL L, obtained from NOF CORPORATION) in an amount (0.3 parts by mass) corresponding to 1% by mass of the radical polymerizable compound. The resultant mixture was mixed for emulsification with a homogenizer (10,000 rpm/5 min, T-50, obtained from IKA Japan, K.K.), followed by interfacial polymerization and radical polymerization at 80° C. for 6 hours. After completion of reaction, the polymerization reaction liquid was left to stand for cooling to room temperature. The polymerized particles were separated through filtration and dried at room temperature under reduced pressure for 24 hours, to obtain spherical particles having an average particle diameter of 2.7 μm. Moreover, the above particles were washed with methyl ethyl ketone, followed by filtration under reduced pressure, to obtain a wet cake of porous particles C.

(Production Example 4 of Porous Particles)

[0176] 800 parts by mass of water, 0.05 parts by mass of a surfactant (NEWREX R, obtained from NOF CORPORATION), and 4 parts by mass of polyvinyl alcohol (degree of polymerization: about 500) (obtained from Wako Pure Chemical Industries, Ltd.) were homogeneously mixed to prepare an aqueous phase. Separately, 11 parts by mass of aluminum bisethyl acetoacetate-monoacethyl acetonate (product name: Aluminum Chelate D, obtained from Kawaken Fine Chemicals Co., Ltd.), 8.8 parts by mass of an adduct of meta-xylylene diisocyanate and trimethylolpropane (product name: TAKENATE D-110N, obtained from MITSUI CHEMICALS, INC.), 2.2 parts by mass of 1,3-bis(isocyanatomethyl)cyclohexane (product name: TAKENATE 600, obtained from MITSUI CHEMICALS, INC.), and 30 parts by mass of ethyl acetate were homogeneously mixed to prepare an oil phase. While the aqueous phase was being stirred with a homogenizer (11,000 rpm), the oil phase was added dropwise to the aqueous phase for 5 minutes. Moreover, the mixture was stirred with a homogenizer for 10 minutes (11,000 rpm), followed by stirring at 60° C. for 12 hours to perform interfacial polymerization. After that, the reaction mixture was cooled to room temperature, and particles were separated with a centrifuge and then filtrated. The obtained particles were dried under reduced pressure for 24 hours to obtain spherical particles having an average particle diameter of 10.4 μm.

[0177] Moreover, the above particles were washed with methyl ethyl ketone, followed by filtration under reduced pressure, to obtain a wet cake of porous particles D.

Use Example 1

[0178] Porous silica (obtained from AGC Si-Tech Co. Ltd., product name: SUNSPHERE H-32) was provided as porous particles E.

Use Example 2

[0179] Triphenylsilanol (obtained from Kanto Chemical Industry Co., Ltd.) was provided as the compound represented by General Formula (2).

Use Example 3

[0180] Tris[(4-trifluoromethyl)phenyl]silanole (obtained from TOKYO CHEMICAL INDUSTRY Co., Ltd.) was provided as the compound represented by General Formula (2).

Example 1-1

[0181] 7 g, on the solid content basis, of the wet cake of porous particles A, which had been obtained in Production Example 1 of Porous Particles, was transferred to a 100 mL three-necked flask equipped with a N.sub.2 introducing tube. 7.0 g of Compound 2 and 30 g of toluene were added to the flask. While N.sub.2 gas was being introduced, the mixture was stirred at 50° C. for 15 minutes in an oil bath, the temperature of which then increased to 110° C. Under stirring, the toluene and the methyl ethyl ketone were distilled off to concentrate the liquid, to hold Compound 2 inside of porous particles A. After completion of concentration, the resultant was cooled and left to stand at room temperature for 24 hours, followed by charging 60 g of cyclohexane and stirring for 1 hour. After that, the mixture was filtrated under reduced pressure, and then a cycle of washing with 30 g of cyclohexane and filtration under reduced pressure was repeated four times. The residue after the filtration was dried under reduced pressure at 60° C. for 4 hours to form porous particles A-2 holding Compound 2 inside thereof.

Example 1-2

[0182] Porous particles A-3 holding Compound 3 inside thereof were formed in the same manner as in Example 1-1 except that Compound 2 was changed to Compound 3.

Examples 2-1 to 2-4

[0183] Porous particles B-1 to B-4 respectively holding Compounds 1 to 4 inside thereof were formed in the same manner as in Example 1-1 except that porous particles A were changed to porous particles B and further Compound 2 was changed to Compounds 1 to 4.

Examples 3-1 to 3-4

[0184] Porous particles C-1 to C-4 respectively holding Compounds 1 to 4 inside thereof were formed in the same manner as in Example 1-1 except that porous particles A were changed to porous particles C and further Compound 2 was changed to Compounds 1 to 4.

Examples 4-1 to 4-4

[0185] Porous particles D-1 to D-4 respectively holding Compounds 1 to 4 inside thereof were formed in the same manner as in Example 1-1 except that porous particles A were changed to porous particles D and further Compound 2 was changed to Compounds 1 to 4.

Example 5-1

[0186] First, 7.0 g of porous particles E was added to a 100 mL three-necked flask and dried at 100° C. under reduced pressure for 3 hours. After cooling, the flask was placed in an oil bath and provided with a N.sub.2 introducing tube and a thermometer. While N.sub.2 gas was being introduced, 7.0 g of Compound 3 and 30 g of toluene were added to the flask, and the mixture was stirred at 50° C. for 15 minutes. The temperature of the oil bath was set to 110° C. Under stirring, the toluene was distilled off to concentrate the liquid, to hold Compound 3 in porous particles E. After completion of concentration, the resultant was cooled and left to stand at room temperature for 24 hours, followed by charging 60 g of cyclohexane and stirring for 1 hour. After filtration under reduced pressure, the resultant was washed with 30 g of cyclohexane, and filtrated again under reduced pressure. The residue after the filtration was dried under reduced pressure at 60° C. for 4 hours to form porous particles E-3 holding Compound 3 inside thereof.

Comparative Synthesis Example 1

[0187] 100 g of a 24% by mass isopropanol solution (solid content: 76% by mass) of Aluminum Chelate D obtained from Kawaken Fine Chemicals Co., Ltd. (aluminum monoacetylacetonate bis(ethyl acetoacetate) was dried at 50° C. under reduced pressure for 24 hours. The resultant was washed with hexane and further dried under reduced pressure at room temperature, to obtain 71.4 g of a reddish-brown viscous solid of aluminum monoacetylacetonate bis(ethyl acetoacetate). This compound was referred to as Comparative Compound 1.

Comparative Example 1-1

[0188] 7 g, on the solid content basis, of the wet cake of porous particles A, which had been obtained in Production Example 1 of Porous Particles, was transferred to a 100 mL three-necked flask equipped with a N.sub.2 introducing tube. 7.0 g of Comparative Compound 1 and 30 g of ethyl acetate were added to the flask. While N.sub.2 gas was being introduced, the mixture was stirred at 50° C. for 15 minutes in an oil bath, the temperature of which was then increased to 80° C. Under stirring, the ethyl acetate was distilled off to concentrate the liquid, to hold Comparative Compound 1 inside of porous particles A. After completion of concentration, the resultant was cooled and left to stand at room temperature for 24 hours, followed by charging 60 g of cyclohexane and stirring for 1 hour. After that, the mixture was filtrated under reduced pressure, and then a cycle of washing with 30 g of cyclohexane and filtration under reduced pressure was repeated four times. The residue after the filtration was dried under reduced pressure at 30° C. for 24 hours to form porous particles A-5 holding Comparative Compound 1 inside thereof.

Comparative Examples 1-2 to 1-5

[0189] Comparative porous particles B-5 to D-5 each holding Comparative Compound 1 inside thereof were formed in the same manner as in Comparative Example 1-1 except that porous particles A were changed to porous particles B to D. Comparative porous particles E-5 were formed in the same manner as in Example 5-1 using Comparative Compound 1.

[0190] The porous particles used and the compounds used in the above Examples are listed in Table 1. The porous particles used and the compounds used in the above Comparative Examples 1-1 to 1-5 are listed in Table 2.

TABLE-US-00001 TABLE 1 Examples 1-1 1-2 2-1 2-2 2-3 2-4 3-1 3-2 3-3 3-4 4-1 4-2 4-3 4-4 5-1 Porous A-2 A-3 B-1 B-2 B-3 B-4 C-1 C-2 C-3 C-4 D-1 D-2 D-3 D-4 E-3 particles obtained Compounds 2 3 1 2 3 4 1 2 3 4 1 2 3 4 3 used Porous A A B B B B C C C C D D D D E particles used

TABLE-US-00002 TABLE 2 Comparative Examples 1-1 1-2 1-3 1-4 1-5 Porous particles obtained A-5 B-5 C-5 D-5 E-5 Compounds used Comparative Compond 1 Comparative Compond 1 Comparative Compond 1 Comparative Compond 1 Comparative Compond 1 Porous particles used A B C D E

Examples 6-1 to 6-15 and Comparative Examples 2-1 to 2-5

[0191] 100 parts by mass of YL980 (obtained from Mitsubishi Chemical Corporation, bisphenol A type epoxy resin), 5 parts by mass of triphenylsilanol (obtained from Kanto Chemical Industry Co., Ltd.), and 2 parts by mass of each of the porous particles formed in the Examples and the Comparative Examples were blended to prepare cationically curable compositions.

[0192] The porous particles used in each of the Examples are listed in Table 3. The porous particles used in each of the Comparative Examples are listed in Table 4.

TABLE-US-00003 TABLE 3 Examples 6-1 6-2 6-3 6-4 6-5 6-6 6-7 6-8 6-9 6-10 6-11 6-12 6-13 6-14 6-15 Porous A-2 A-3 B-1 B-2 B-3 B-4 C-1 C-2 C-3 C-4 D-1 D-2 D-3 D-4 E-3 particles used

TABLE-US-00004 TABLE 4 Comparative Examples 2-1 2-2 2-3 2-4 2-5 Porous particles used A-5 B-5 C-5 D-5 E-5

Comparative Examples 2-6 to 2-10

[0193] Cationically curable compositions were prepared in the same manner as in Examples 6-1 to 6-15 and Comparative Examples 2-1 to 2-5 except that the porous particles were changed to 2 parts by mass of each of Compounds 1 to 4 and Comparative Compound 1.

[0194] The compounds used in the Comparative Examples are listed in Table 5.

TABLE-US-00005 TABLE 5 Comparative Examples 2-6 2-7 2-8 2-9 2-10 Compounds used 1 2 3 4 Comparative Compound 1

[0195] Each (5 mg) of the cationically curable compositions prepared in Examples 6-1 to 6-15 and Comparative Examples 2-1 to 2-10 was placed in an aluminum container having a diameter of 5 mm for DSC6200, followed by performing differential scanning calorimetry. The exothermic peak temperature of the DSC measurement was evaluated.

[0196] As well known in the art, cationic curing is an exothermic reaction, and an exothermic peak temperature obtained in differential scanning calorimetry reflects curing performance of cationic curing and the lower exothermic peak temperature is more desirable.

[0197] The conditions for the differential scanning calorimetry are as follows.

[Measuring Conditions]

[0198] Heating rate: 10° C./min (25° C. to 300° C.) [0199] N.sub.2 gas: 100 mL/min

[0200] Each of the cationically curable compositions prepared in Examples 6-1 to 6-15 and Comparative Examples 2-1 to 2-10 was stored in a sealed container for 1 day (24 hours) at 25° C., and the reaction rate during the storage was estimated by comparing the exothermic values of differential scanning calorimetry before and after the storage. The results are presented in Tables 6 and 7 together with the results of curing performance.

[0201] Note that, the reaction rate is determined by the following formula.

Reaction rate (%)=100×[(exothermic value before storage)−(exothermic value after storage)]/(exothermic value before storage)

TABLE-US-00006 TABLE 6 Examples 6-1 6-2 6-3 6-4 6-5 6-6 6-7 6-8 6-9 6-10 6-11 6-12 6-13 6-14 6-15 Porous A-2 A-3 B-1 B-2 B-3 B-4 C-1 C-2 C-3 C-4 D-1 D-2 D-3 D-4 E-3 particles used Exothermic 115 118 103 104 108 107 95.3 96.2 101 98.5 109 10 115 113 102 peak temp. [° C.] Reaction 4.9 5.3 9.6 8.9 6.4 6.8 10.2 11.7 8.5 7.9 5.2 5.8 3.2 4.7 6.0 rate [%]

TABLE-US-00007 TABLE 7 Comparative Examples 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 2-10 Porous A-5 B-5 C-5 D-5 E-5 — — — — — particles used Compounds — — — — — 1 2 3 4 Comp. used Compd. 1 Exothermic 147.3 120.5 110.3 128 112.3 81.2 75.2 76.3 79.2 95.3 peak temp. [° C.] Reaction 1.4 2.5 4.8 3.6 3.9 30.2 35.4 39.2 35.6 31.2 rate [%]

[0202] From the results of Tables 6 and 7, in comparison to Comparative Examples 2-6 to 2-10 in which the compound was added alone, the Examples increased in the exothermic peak temperature but improved remarkably in storage stability, suggesting that latent characteristics were secured by enclosing the compound in the porous particles.

[0203] The comparisons between the compositions containing the same porous particles (i.e., Examples 6-1 and 6-2 in comparison to Comparative Example 2-1, Examples 6-3 to 6-6 in comparison to Comparative Example 2-2, Examples 6-7 to 6-10 in comparison to Comparative Example 2-3, Examples 6-11 to 6-14 in comparison to Comparative Example 2-4, and Example 2-5 in comparison to Comparative Example 2-5) indicate that the peak temperatures in all the comparisons are lowered in the porous particles holding therein the compounds of the present invention. That is, the porous particles holding therein the compounds of the present invention (cationic curing agents) are found to improve curing performance.

Example 7-1

[0204] 1.0 g of n-propyltrimethoxysilane (KBM-3033, obtained from Shin-Etsu Chemical Co., Ltd.) was dissolved in 9 g of cyclohexane to prepare a surface-inactivating treatment liquid. To this treatment liquid was charged 1.0 g of porous particles A-2 formed in Example 1-1. The resultant mixture was stirred at 30° C. for 20 hours. After that, the mixture was filtrated under reduced pressure while being washed with 10 g of cyclohexane, to separate the porous particles. The porous particles were dried at 40° C. under reduced pressure for 6 hours to form surface-treated porous particles A-2-1.

Examples 7-2 to 7-15

[0205] Surface-treated porous particles listed in Table 8 were formed in the same manner as in Example 7-1 except that the porous particles used were changed as described in Table 8.

Comparative Examples 3-1 to 3-5

[0206] Surface-treated porous particles listed in Table 9 were formed in the same manner as in Example 7-1 except that the porous particles used were changed as described in Table 9.

TABLE-US-00008 TABLE 8 Examples 7-1 7-2 7-3 7-4 7-5 7-6 7-7 7-8 7-9 7-10 7-11 7-12 7-13 7-14 7-15 Porous A-2-1 A-3-1 B-1-1 B-2-1 B-3-1 B-4-1 C-1-1 C-2-1 C-3-1 C-4-1 D-1-1 D-2-1 D-3-1 D-4-1 E-3-1 particles formed Porous A-2 A-3 B-1 B--2 B-3 B-4 C-1 C-2 C-3 C-4 D-1 D-2 D-3 D-4 E-3 particles used

TABLE-US-00009 TABLE 9 Comparative Examples 3-1 3-2 3-3 3-4 3-5 Porous A-5-1 B-5-1 C-5-1 D-5-1 E-5-1 particles formed Porous A-5 B-5 C-5 D-5 E-5 particles used

Examples 8-1 to 8-15 and Comparative Examples 4-1 to 4-5

[0207] 60 parts by mass of YL980 (obtained from Mitsubishi Chemical Corporation, bisphenol A type epoxy resin), 15 parts by mass of CELLOXIDE 2021P (obtained from DAICEL CORPORATION), 25 parts by mass of ARONE OXETANE OXT-221 (obtained from TOAGOSEI CO. LTD.), 5 parts by mass of triphenylsilanol (obtained from Kanto Chemical Industry Co., Ltd.), and 2 parts by mass of the porous particles formed in each of Examples 7-1 to 7-15 and Comparative Examples 3-1 to 3-5 were blended, to prepare cationically curable compositions of Examples 8-1 to 8-15 and Comparative Examples 4-1 to 4-5.

[0208] The porous particles used in each of the Examples are listed in Table 10. The porous particles used in each of the Comparative Examples are listed in Table 11.

TABLE-US-00010 TABLE 10 Examples 8-1 8-2 8-3 8-4 8-5 8-6 8-7 8-8 8-9 8-10 8-11 8-12 8-13 8-14 8-15 Porous A-2-1 A- 3-1 B-1-1 B-2-1 B-3-1 B-4-1 C-1-1 C-2-1 C-3-1 C-4-1 D-1-1 D-2-1 D-3-1 D-4-1 E-3-1 particles used

TABLE-US-00011 TABLE 11 Comparative Examples 4-1 4-2 4-3 4-4 4-5 Porous A-5-1 B-5-1 C-5-1 D-5-1 E-5-1 particles used

[0209] In the same manner as described above, each (5 mg) of the cationically curable compositions prepared in Examples 8-1 to 8-15 and Comparative Examples 4-1 to 4-5 was placed in an aluminum container having a diameter of 5 mm for DSC6200, followed by performing differential scanning calorimetry. The exothermic peak temperature of the DSC measurement was evaluated.

[0210] Each of the cationically curable compositions prepared in Examples 8-1 to 8-15 and Comparative Examples 4-1 to 4-5 was stored in a sealed container for 1 day (24 hours) at 25° C., and the reaction rate during the storage was estimated by comparing the exothermic values of differential scanning calorimetry before and after the storage. The results are presented in Tables 12 and 13 together with the results of curing performance.

[0211] Note that, the reaction rate is determined by the following formula.

Reaction rate (%)=100×[(exothermic value before storage)−(exothermic value after storage)]/(exothermic value before storage)

TABLE-US-00012 TABLE 12 Examples 8-1 8-2 8-3 8-4 8-5 8-6 8-7 8-8 8-9 8-10 8-11 8-12 8-13 8-14 8-15 Porous A-2-1 A-3-1 B-1-1 B-2-1 B-3-1 B-4-1 C-1-1 C-2-1 C-3-1 C-4-1 D-1-1 D-2-1 D-3-1 D-4-1 E-3-1 particles used Exothermic 127 131 118 121 123 123 108 105 109 112 121 124 129 125 125 peak temp. [° C.] Reaction 0.8 1.2 1.3 1.8 0.9 0.5 2.1 2.4 1.9 3.1 1.2 0.6 0.7 0.9 3.8 rate [%]

TABLE-US-00013 TABLE 13 Comparative Examples 4-1 4-2 4-3 4-4 4-5 Porous A-5-1 B-5-1 C-5-1 D-5-1 E-5-1 particles used Exothermic 153.2 138.5 130.2 150.8 135.6 peak temp. [° C.] Reaction 0.4 1.3 2.1 0.9 3.4 rate [%]

[0212] From the results of Tables 12 and 13, the comparisons between the compositions containing the same porous particles (i.e., Examples 8-1 and 8-2 in comparison to Comparative Example 4-1, Examples 8-3 to 8-6 in comparison to Comparative Example 4-2, Examples 8-7 to 8-10 in comparison to Comparative Example 4-3, Examples 8-11 to 8-14 in comparison to Comparative Example 4-4, and Example 8-5 in comparison to Comparative Example 4-5) indicate that the peak temperatures in all the comparisons are lowered in the cationic curing agents of the present invention. That is, the cationic curing agents of the present invention are found to improve curing performance.

[0213] In addition, almost no difference is between the present invention and the Comparative Example in the reaction rate after storage for 1 day at 25° C., suggesting that the cationic curing agent of the present invention has increased curing performance without involving impaired storage stability. That is, the cationic curing agent of the present invention is found to improve curing performance without impairing latent characteristics.

Example 11-1

[0214] 5.2 g of Compound 2, 5.1 g of triphenylsilanol, and 30 g of methyl ethyl ketone were added to a 100 mL three-necked flask equipped with a N.sub.2 introducing tube, and the mixture was stirred in an oil bath at 50° C. for 15 minutes. After that, 7 g, on the solid content basis, of the wet cake of porous particles A, which had been obtained in Production Example 1 of Porous Particles, was charged to the flask. While N.sub.2 gas was being introduced, the temperature of the oil bath was increased to 80° C. Under stirring, the methyl ethyl ketone was distilled off to concentrate the liquid, to hold a mixture of Compound 2 and triphenylsilanol inside of porous particles A. After completion of concentration, the resultant was cooled and left to stand at room temperature for 24 hours, followed by charging 60 g of cyclohexane and stirring for 1 hour. After that, the mixture was filtrated under reduced pressure, and then a cycle of washing with 30 g of cyclohexane and filtration under reduced pressure was repeated four times. The residue after the filtration was dried under reduced pressure at 60° C. for 4 hours to form porous particles AA-2 holding the mixture of Compound 2 and triphenylsilanol inside thereof.

Example 11-2

[0215] Porous particles AA-3 holding a mixture of Compound 3 and triphenylsilanol inside thereof were formed in the same manner as in Example 11-1 except that Compound 2 was changed to 5.5 g of Compound 3 and the amount of triphenylsilanol was changed to 5.0 g.

Examples 12-1 to 12-4

[0216] Porous particles BB-1 to BB-4 each holding a mixture of each of Compounds 1 to 4 and triphenylsilanol inside thereof were formed in the same manner as in Example 11-1 except that porous particles A were changed to porous particles B and further the kind of the compound and the amount of the compound charged were changed as described in Table 14-1.

TABLE-US-00014 TABLE 14-1 Examples 12-1 12-2 12-3 12-4 Compound of Kind 1 2 3 4 General Formula (1) Amount charged [g] 5.0 5.2 5.5 5.0 Amount of Comound of General Formula (2) 5.3 5.1 5.0 5.3 (triphenylsilanol) charged [g]

Examples 12-5 to 12-8

[0217] Porous particles BB-6 to BB-9 each holding a mixture of each of Compounds 1 to 4 and tris[(4-trifluoromethyl)phenyl]silanol inside thereof were formed in the same manner as in Example 11-1 except that porous particles A were changed to porous particles B and further the kind of the compound and the amount of the compound charged were changed as described in Table 14-1.

TABLE-US-00015 TABLE 14-2 Examples 12-5 12-6 12-7 12-8 Compound of Kind 1 2 3 4 General Formula (1) Amount charged [g] 5.0 5.0 5.0 5.0 Amount of Comound of General Formula (2) 9.2 8.5 7.9 9.2 tris[(4-trifluoromethyl)phenyl]silanol charged [g]

Examples 13-1 to 13-4

[0218] Porous particles CC-1 to CC-4 each holding a mixture of each of Compounds 1 to 4 and triphenylsilanol inside thereof were formed in the same manner as in Example 11-1 except that porous particles A were changed to porous particles C and further the kind of the compound and the amount of the compound charged were changed as described in Table 15.

TABLE-US-00016 TABLE 15 Examples 13-1 13-2 13-3 13-4 Compound of Kind 1 2 3 4 General Formula (1) Amount charged [g] 5.0 5.2 5.5 5.0 Amount of Compound of General Formula (2) 5.3 5.1 5.0 5.3 (triphenylsilanol) charged [g]

Examples 14-1 to 14-4

[0219] Porous particles DD-1 to DD-4 each holding a mixture of each of Compounds 1 to 4 and triphenylsilanol inside thereof were formed in the same manner as in Example 11-1 except that porous particles A were changed to porous particles D and further the kind of the compound and the amount of the compound charged were changed as described in Table 16.

TABLE-US-00017 TABLE 16 Examples 14-1 14-2 14-3 14-4 Compound of Kind 1 2 3 4 General Formula (1) Amount charged [g] 5.0 5.2 5.5 5.0 Amount of Compound of General Formula (2) 5.3 5.1 5.0 5.3 (triphenylsilanol) charged [g]

Example 15-1

[0220] First, 7.0 g of porous particles E was added to a 100 mL three-necked flask and dried at 100° C. under reduced pressure for 3 hours. After cooling, the flask was placed in an oil bath and provided with a N.sub.2 introducing tube and a thermometer. While N.sub.2 gas was being introduced, 5.5 g of Compound 3, 5.0 g of triphenylsilanol, and 30 g of ethyl acetate were added to the flask, and the mixture was stirred at 50° C. for 15 minutes. The temperature of the oil bath was set to 80° C. Under stirring, the ethyl acetate was distilled off to concentrate the liquid, to hold a mixture of Compound 3 and triphenylsilanol in porous particles E. After completion of concentration, the resultant was cooled and left to stand at room temperature for 24 hours, followed by charging 60 g of cyclohexane and stirring for 1 hour. After filtration under reduced pressure, the resultant was washed with 30 g of cyclohexane, and filtrated again under reduced pressure. The residue after the filtration was dried under reduced pressure at 60° C. for 4 hours to form porous particles EE-3 holding the mixture of Compound 3 and triphenylsilanol inside thereof.

Comparative Production Example

[0221] 100 g of a 24% by mass isopropanol solution (solid content: 76% by mass) of Aluminum Chelate D obtained from Kawaken Fine Chemicals Co., Ltd. (aluminum monoacetylacetonate bis(ethyl acetoacetate) was dried at 50° C. under reduced pressure for 24 hours. The resultant was washed with hexane and further dried under reduced pressure at room temperature, to obtain 71.4 g of a reddish-brown viscous solid of aluminum monoacetylacetonate bis(ethyl acetoacetate). This compound was referred to as Comparative Compound 1.

Comparative Example 11-1

[0222] 7 g, on the solid content basis, of the wet cake of porous particles A, which had been obtained in Production Example 1 of Porous Particles, was transferred to a 100 mL three-necked flask equipped with a N.sub.2 introducing tube. 7.0 g of Comparative Compound 1 and 30 g of ethyl acetate were added to the flask. While N.sub.2 gas was being introduced, the mixture was stirred at 50° C. for 15 minutes in an oil bath, the temperature of which was then increased to 80° C. Under stirring, the ethyl acetate was distilled off to concentrate the liquid, to hold Comparative Compound 1 inside of porous particles A After completion of concentration, the resultant was cooled and left to stand at room temperature for 24 hours, followed by charging 60 g of cyclohexane and stirring for 1 hour. After that, the mixture was filtrated under reduced pressure, and then a cycle of washing with 30 g of cyclohexane and filtration under reduced pressure was repeated four times. The residue after the filtration was dried under reduced pressure at 30° C. for 24 hours to form porous particles AA-5 holding Comparative Compound 1 inside thereof.

Comparative Examples 11-2 to 11-4

[0223] Comparative porous particles BB-5 to DD-5 each holding Comparative Compound 1 inside thereof were formed in the same manner as in Comparative Example 11-1 except that porous particles A were changed to porous particles B to D.

[0224] The porous particles used and the compound used in the above Examples are listed in Tables 17-1 and 17-2. The porous particles used and the compound used in Comparative Examples 11-1 to 11-4 are listed in Table 18.

TABLE-US-00018 TABLE 17-1 Examples 11-1 11-2 12-1 12-2 12-3 12-4 12-5 12-6 12-7 12-8 Porous particles AA-2 AA-3 BB-1 BB-2 BB-3 BB-4 BB-6 BB-7 BB-8 BB-9 obtained General Formula (1) 2 3 1 2 3 4 5 6 7 8 compound used Porous particles used A A B B B B B B B B General Formula (2) Triphenylsilanol Tris[(4-trifluoromethyl)phenyl]silanol compound used

TABLE-US-00019 TABLE 17-2 Examples 13-1 13-2 13-3 13-4 14-1 14-2 14-3 14-4 15-1 Porous particles obtained CC-1 CC-2 CC-3 CC-4 DD-1 DD-2 DD-3 DD-4 EE-3 General Formula (1) 1 2 3 4 1 2 3 4 3 compound used Porous particles used C C C C D D D D E General Formula (2) Triphenylsilanol compound used

TABLE-US-00020 TABLE 18 Comparative Examples 11-1 11-2 11-3 11-4 Porous AA-5 BB-5 CC-5 DD-5 particles obtained Compounds Comp. Comp. Comp. Comp. used Compd. 1 Compd. 1 Compd. 1 Compd. 1 Porous A B C D particles used

Examples 16-1 to 16-19 and Comparative Examples 12-1 to 12-4

[0225] 100 parts by mass of YL980 (obtained from Mitsubishi Chemical Corporation, bisphenol A type epoxy resin), 5 parts by mass of triphenylsilanol (obtained from Kanto Chemical Industry Co., Ltd.), and 2 parts by mass of each of the porous particles formed in the Examples and the Comparative Examples were blended to prepare cationically curable compositions.

[0226] The porous particles used in each of the Examples are listed in Tables 19-1 and 19-2. The porous particles used in each of the Comparative Examples are listed in Table 20.

TABLE-US-00021 TABLE 19-1 Examples 16-1 16-2 16-3 16-4 16-5 16-6 16-7 16-8 16-9 16-10 Porous AA-2 AA-3 BB-1 BB-2 BB-3 BB-4 CC-1 CC-2 CC-3 CC-4 particles used

TABLE-US-00022 TABLE 19-2 Examples 16-11 16-12 16-13 16-14 16-15 16-16 16-17 16-18 16-19 Porosis particles used DD-1 DD-2 DD-3 DD-4 EE-3 BB-6 BB-7 BB-8 BB-9

TABLE-US-00023 TABLE 20 Comparative Examples 12-1 12-2 12-3 12-4 Porous AA-5 BB-5 CC-5 DD-5 particles used

[0227] Each (5 mg) of the cationically curable compositions prepared in Examples 16-1 to 16-19 and Comparative Examples 12-1 to 12-4 was placed in an aluminum container having a diameter of 5 mm for DSC6200, followed by performing differential scanning calorimetry. The exothermic peak temperature of the DSC measurement was evaluated.

[0228] As well known in the art, cationic curing is an exothermic reaction, and an exothermic peak temperature obtained in differential scanning calorimetry reflects curing performance of cationic curing and the lower exothermic peak temperature is more desirable.

[0229] The conditions for the differential scanning calorimetry are as follows.

[Measuring Conditions]

[0230] Heating rate: 10° C./min (25° C. to 300° C.) [0231] N.sub.2 gas: 100 mL/min

[0232] Each of the cationically curable compositions prepared in Examples 16-1 to 16-19 and Comparative Examples 12-1 to 12-4 was stored in a sealed container for 1 day (24 hours) at 25° C., and the reaction rate during the storage was estimated by comparing the exothermic values of differential scanning calorimetry before and after the storage. The results are presented in Tables 21-1, 21-2, and 22 together with the results of curing performance.

[0233] Note that, the reaction rate is determined by the following formula.

Reaction rate (%)=100×[(exothermic value before storage)−(exothermic value after storage)]/(exothermic value before storage)

TABLE-US-00024 TABLE 21-1 Examples 16-1 16-2 16-3 16-4 16-5 16-6 16-7 16-8 16-9 16-10 Porous particles AA-2 AA-3 BB-1 BB-2 BB-3 BB-4 CC-1 CC-2 CC-3 CC-4 used Exothermic peak 108.7 105.3 98.4 99.7 102.8 105.7 90.5 92.1 95.7 94.2 temp. [° C.] Reaction rate [%] 6.2 7.4 9.8 10.5 9.7 5.2 12.1 10.9 11.4 15.2

TABLE-US-00025 TABLE 21-2 Examples 16-11 16-12 16-13 16-14 16-15 16-16 16-17 16-18 16-19 Porous particles used DD-1 DD-2 DD-3 DD-4 EE-3 BB-6 BB-7 BB-8 BB-9 Exothermic peak temp. [° C.] 103.9 109.9 109.1 112.3 99.8 93.4 95.2 98.1 98.4 Reaction rate [%] 4.8 7.9 6.7 3.2 9.1 10.2 9.8 6.9 9.8

TABLE-US-00026 TABLE 22 Comparative Examples 12-1 12-2 12-3 12-4 Porous particles AA-5 BB-5 CC-5 DD-5 used Exothermic peak 147.3 120.5 110.3 128.2 temp. [° C.] Reaction rate [%] 1.4 2.5 4.8 3.6

[0234] From the results of Tables 21-1, 21-2, and 22, the comparisons between the compositions containing the same porous particles (i.e., Examples 16-1 and 16-2 in comparison to Comparative Example 12-1, Examples 16-3 to 16-6 in comparison to Comparative Example 12-2, Examples 16-7 to 16-10 in comparison to Comparative Example 12-3, and Examples 16-11 to 16-14 in comparison to Comparative Example 12-4) indicate that the peak temperatures in all the comparisons are lowered in the porous particles holding the compounds of the present invention. That is, the porous particles of the present invention (cationic curing agents) are found to improve curing performance. The comparisons between the particles containing different compounds of General Formula (2) (comparisons between Examples 16-3 to 16-6 and Examples 16-16 to 16-19) suggest that those using tris[(4-trifluoromethyl)phenyl]silanol, in which an electron attractive trifluoromethyl group is added to the phenyl group of triphenylsilanol, have exothermic peaks at lower temperatures and can improve curing performance.

Example 17-1

[0235] 1.0 g of n-propyltrimethoxysilane (KBM-3033, obtained from Shin-Etsu Chemical Co., Ltd.) was dissolved in 9 g of cyclohexane to prepare a surface-inactivating treatment liquid. To this treatment liquid was charged 1.0 g of porous particles AA-2 formed in Example 12-1. The resultant mixture was stirred at 30° C. for 20 hours. After that, the mixture was filtrated under reduced pressure while being washed with 10 g of cyclohexane, to separate the porous particles. The porous particles were dried at 40° C. under reduced pressure for 6 hours to form surface-treated porous particles AA-2-1.

Examples 17-2 to 17-19

[0236] Surface-treated porous particles of Examples 17-2 to 17-19 were formed in the same manner as in Example 14-1 except that the porous particles used were changed as described in Tables 23-1 and 23-2.

Comparative Examples 13-1 to 13-4

[0237] Surface-treated comparative porous particles of Comparative Examples 13-1 to 13-4 were formed in the same manner as in Example 17-1 except that the porous particles used were changed as described in Table 24.

TABLE-US-00027 TABLE 23-1 Examples 17-1 17-2 17-3 1 7-4 17-5 17-6 17-7 17-8 17-9 17-10 Porous particles AA-2-1 AA-3-1 BB-1-1 BB-2-1 BB-3-1 BB-4-1 CC-1-1 CC-2-1 CC-3-1 CC-4-1 formed Porous particles AA-2 AA-3 BB-1 BB-2 BB-3 BB-4 CC-1 CC-2 CC-3 CC-4 used

TABLE-US-00028 TABLE 23-2 Examples 17-11 17-12 17-13 17-14 17-15 17-16 17-17 17-18 17-19 Porous particles formed DD-1-1 DD-2-1 DD-3-1 DD-4-1 EE-3-1 BB-6-1 BB-7-1 BB-8-1 BB-9-1 Porous particles used DD-1 DD-2 DD-3 DD-4 EE-3 BB-6 BB-7 BB-8 BB-9

TABLE-US-00029 TABLE 24 Comparative Examples 13-1 13-2 13-3 13-4 Porous particles AA-5-1 BB-5-1 CC-5-1 DD-5-1 formed Porous particles AA-5 BB-5 CC-5 DD-5 used

Examples 18-1 to 18-19 and Comparative Examples 14-1 to 14-4

[0238] 60 parts by mass of YL980 (obtained from Mitsubishi Chemical Corporation, bisphenol A type epoxy resin), 15 parts by mass of CELLOXIDE 2021P (obtained from DAICEL CORPORATION), 25 parts by mass of ARONE OXETANE OXT-221 (obtained from TOAGOSEI CO. LTD.), 5 parts by mass of triphenylsilanol (obtained from Kanto Chemical Industry Co., Ltd.), and 2 parts by mass of the porous particles formed in each of Examples 17-1 to 17-19 and Comparative Examples 13-1 to 13-4 were blended, to prepare cationically curable compositions of Examples 18-1 to 18-19 and Comparative Examples 14-1 to 14-4.

[0239] The porous particles used in each of the Examples are listed in Tables 25-1 and 25-2. The porous particles used in each of the Comparative Examples are listed in Table 25-3.

Examples 19-1 to 19-4 and Comparative Example 15-1

[0240] 60 parts by mass of YL980 (obtained from Mitsubishi Chemical Corporation, bisphenol A type epoxy resin), 15 parts by mass of CELLOXIDE 2021P (obtained from DAICEL CORPORATION), 25 parts by mass of ARONE OXETANE OXT-221 (obtained from TOAGOSEI CO. LTD.), 5 parts by mass of tris[(4-trifluoromethyl)phenyl]silanole (obtained from TOKYO CHEMICAL INDUSTRY Co., Ltd.), and 2 parts by mass of the porous particles formed in each of Examples 17-3 to 17-6 and Comparative Example 13-2 were blended, to prepare cationically curable compositions of Examples 19-1 to 19-4 and Comparative Example 15-1.

TABLE-US-00030 TABLE 25-1 Examples 18-1 18-2 18-3 18-4 18-5 18-6 18-7 18-8 18-9 18-10 Porous AA-2-1 AA-3-1 BB-1-1 BB-2-1 BB-3-1 BB-4-1 CC-1-1 CC-2-1 CC-3-1 CC-4-1 particles used

TABLE-US-00031 TABLE 25-2 Examples 18-11 18-12 18-13 18-14 18-15 18-16 18-17 18-18 18-19 Porous particles used DD-1-1 DD-2-1 DD-3-1 DD-4-1 EE-3-1 BB-6-1 BB-7-1 BB-8-1 BB-9-1

TABLE-US-00032 TABLE 25-3 Comparative Examples 14-1 14-2 14-3 14-4 Porous AA-5-1 BB-5-1 CC-5-1 DD-5-1 particles used

TABLE-US-00033 TABLE 26 Examples Comp. Ex. 19-1 19-2 19-3 19-4 15-1 Porous BB-1-1 BB-2-1 BB-3-1 BB-4-1 BB-5-1 particles used

[0241] In the same manner as described above, each (5 mg) of the cationically curable compositions prepared in Examples 18-1 to 18-19 and 19-1 to 19-4 and Comparative Examples 14-1 to 14-4 and 15-1 was placed in an aluminum container having a diameter of 5 mm for DSC6200, followed by performing differential scanning calorimetry. The exothermic peak temperature of the DSC measurement was evaluated.

[0242] Each of the cationically curable compositions prepared in Examples 18-1 to 18-19 and 19-1 to 19-4 and Comparative Examples 14-1 to 14-4 and 15-1 was stored in a sealed container for 1 day (24 hours) at 25° C., and the reaction rate during the storage was estimated by comparing the exothermic values of differential scanning calorimetry before and after the storage. The results are presented in Tables 27-1, 27-2, 27-3, and 28 together with the results of curing performance.

[0243] Note that, the reaction rate is determined by the following formula.

Reaction rate (%)=100×[(exothermic value before storage)−(exothermic value after storage)]/(exothermic value before storage)

TABLE-US-00034 TABLE 27-1 Examples 18-1 18-2 18-3 18-4 18-5 18-6 18-7 18-8 18-9 18-10 Porous particles AA-2-1 AA-3-1 BB-1-1 BB-2-1 BB-3-1 BB-4-1 CC-1-1 CC-2-1 CC-3-1 CC-4-1 used Exothermic peak 120.4 125.7 113.2 112.9 118.6 116.3 98.3 95.2 101.4 103.4 temp. [° C.] Reaction rate [%] 0.3 2.1 0.9 1.8 2.2 0.7 3.1 3.5 2.1 0.7

TABLE-US-00035 TABLE 27-2 Examples 18-11 18-12 18-13 18-14 18-15 18-16 18-17 18-18 18-19 Porous particles used DD-1-1 DD-2-1 DD-3-1 DD-4-1 EE-3-1 BB-6-1 BB-7-1 BB-8-1 BB-9-1 Exothermic peak temp. [° C.] 115.8 119.7 125.3 117.4 122.1 105.3 103.2 109.2 109.8 Reaction rate [%] 0.9 1.2 1.4 0.8 4.1 1.3 2.1 0.8 1.8

TABLE-US-00036 TABLE 27-3 Comparative Examples 14-1 14-2 14-3 14-4 Porous particles AA-5-1 BB-5-1 CC-5-1 DD-5-1 used Exothermic peak 153.2 138.5 130.2 150.8 temp. [° C.] Reaction rate [%] 0.4 1.3 2.1 0.9

TABLE-US-00037 TABLE 28 Comp. Examples Ex. 19-1 19-2 19-3 19-4 15-1 Porous particles used BB-1-1 BB-2-1 BB-3-1 BB-4-1 BB-5-1 Exothermic peak 105.3 100.2 108.9 107.8 130.2 temp. [° C.] Reaction rate [%] 0.8 2.2 0.5 2.5 0.9

[0244] From the results of Tables 27-1, 27-2, 27-3, and 28, the comparisons between the compositions containing the same porous particles (i.e., Examples 18-1 and 18-2 in comparison to Comparative Example 14-1, Examples 18-3 to 18-6 in comparison to Comparative Example 14-2, Examples 18-7 to 18-10 in comparison to Comparative Example 14-3, and Examples 18-11 to 18-14 in comparison to Comparative Example 14-4) indicate that the peak temperatures in all the comparisons are lowered in the porous particles holding therein the compounds of the present invention. That is, the cationic curing agents of the present invention are found to improve curing performance.

[0245] The comparisons between the particles containing different compounds of General Formula (2) (comparisons between Examples 18-3 to 18-6 and Examples 18-16 to 18-19) suggest that those using tris[(4-trifluoromethyl)phenyl]silanol, in which an electron attractive trifluoromethyl group is added to the phenyl group of triphenylsilanol, have exothermic peaks at lower temperatures and can improve curing performance.

[0246] In comparison to Comparative Example 15-1, Examples 19-1 to 19-4, in which the compound of General Formula (2) contained in the cationically curable compositions was tris[(4-trifluoromethyl)phenyl]silanol, also indicate that the peak temperatures are lowered in the porous particles holding therein the compounds of the present invention. Even in comparison to Examples 18-3 to 18-6 in which triphenylsilanol was blended, the peak temperatures are lowered, suggesting that the addition of an electron attractive group to the phenyl group of triphenylsilanol allows for better curing performance.

[0247] In addition, almost no difference is between the present invention and the Comparative Example in the reaction rate after storage for 1 day at 25° C., suggesting that the porous particles of the present invention have increased curing performance without impairing storage stability. That is, the cationic curing agent of the present invention is found to improve curing performance without impairing latent characteristics. Also, this effect is found to remain unchanged even if the compound of General Formula (2) in the cationically curable composition is changed from triphenylsilanol to tris[(4-trifluoromethyl)phenyl]silanol.

INDUSTRIAL APPLICABILITY

[0248] The cationic curing agent of the present invention is suitably used as a latent curing agent of a cationically curable composition.

[0249] The cationically curable composition of the present invention is suitably used as a cationically curable composition of latent curing.

CATIONIC CURING AGENT, METHOD FOR PRODUCING SAME AND CATIONICALLY CURABLE COMPOSITION

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