JP2000080154A - Curing agent and cure accelerator for resin and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curing agent and a cure accelerator reduced in the tendency to sublime or to decompose and giving a resin composition having improved heat stability and a prolonged pot life when added to a resin by selecting a clathrate compound of a tetrakisphenol compound with a special organic compound. SOLUTION: The tetrakisphenol compound is represented by formula I (wherein X is (CH2)n; n is 0, 1, 2, or 3; and R1 to R8 are each hydrogen, a lower alkyl, a (substituted) phenyl, a halogen, or a lower alkoxyl). The organic compound used is represented by formula II (wherein R9 to R12 are each hydrogen, a lower alkyl, a (substituted) phenyl, or a heterocyclic group or a lower alkoxyl, provided that R9 and R11 together with the carbon and nitrogen atoms to which they are attached may form a five- to ten-membered ring, and R10 and R12 together with the nitrogen atoms to which they are attached may form a five- to seven-membered heterocyclic ring containing still another ring nitrogen atom).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition, and more particularly to a resin curing agent and a resin curing accelerator using a tetrakisphenol compound.

[0002]

2. Description of the Related Art Epoxy resins, urethane resins and acrylic resins have excellent chemical resistance, corrosion resistance, mechanical properties, thermal properties, excellent adhesion to various substrates, electrical properties, and workability regardless of the environment. It is widely used for adhesives, paints, electric metal materials, composite materials, and the like. The epoxy resin composition, urethane resin composition and acrylic resin are composed of a combination of a resin prepolymer having two or more reactive groups in one molecule and a curing agent, and further include a curing accelerator, a denaturing agent, and a filling agent depending on the application. Agents are often added. It is known that the properties of a cured resin greatly depend on the curing agent, and various curing agents have been used for industrial purposes. Epoxy resin compositions, urethane resin compositions and acrylic resin compositions can be broadly divided into one-pack and two-pack types depending on the method of use.
The former one-pack type can cure the composition itself by heating, pressurizing, and leaving it to stand. On the other hand, in the two-pack type, after mixing a base material and a curing agent or a curing accelerator at the time of use, the mixture can be cured by heating, pressurizing, or standing. Epoxy resin compositions, urethane resin compositions, and acrylic resin compositions are usually two-packs, and these two-packs are cumbersome and inefficient when viewed from the work surface, but the strength, thermal properties, It is widely used in the field of electric components, automobiles, and aircraft because it has many excellent properties in terms of electrical characteristics and the like. However, in the two-pack type, (1) the pot life, that is, the time for maintaining the state in which the composition prepared for curing can be used is short, and a part of the reaction starts due to the preparation, and the viscosity of the system increases. There are problems such as a decrease in workability, and (2) a decrease in physical properties due to a mixing mistake or incomplete preparation, and a one-pack type latent curing agent and a curing accelerator are desired. The latent curing agent and the curing accelerator are those in which the curing agent and the curing accelerator mixed in the resin are stable at room temperature and cause a curing reaction by the action of heat or the like. The action of heat, light, pressure, etc. can be considered to initiate the curing reaction,
A lot of heat is used. Although microcapsules are used as a method for stabilizing the curing agent and the curing accelerator, there is a problem in terms of stability such that the mechanical strength is weak and the blending for preparing the resin composition cannot be tolerated.

[0003] Further, the curing agent includes (1) an addition-type curing agent in which the curing agent molecules are necessarily incorporated into the cured resin by reacting with the reactive group of the resin, and (2) the curing agent molecules are contained in the resin. There are a polymerizable curing agent which acts on the reactive group of the resin catalytically without being incorporated and causes a polymerization addition reaction between oligomers, and (3) a photoinitiated curing agent which cures by irradiation with ultraviolet rays. Whichever method is used,
It is most important to carry out the polymerization addition reaction more uniformly and promptly under certain conditions in order to obtain a stable cured product. However, these existing curing agents alone (1)
The curing reaction stops halfway with an increase in resin viscosity, (2) there are many factors inhibiting the curing reaction, (3) severe conditions are required to complete the curing reaction,
(4) There is a problem that a large amount of a curing agent is required in order to make the curing reaction uniform, and a curing accelerator that makes it possible to perform the polymerization addition reaction uniformly and promptly under mild conditions has been developed. Is desired. The hardening accelerator is used to increase the hardening speed of the hardening agent for hardening the resin and to make the hardening reaction prompt and smooth. In addition-type curing agents such as primary and secondary amines, alcohol or phenol is used as a curing accelerator for accelerating the polymerization addition reaction.
A polymerization-type curing agent such as imidazole has a problem in versatility, such as inhibition of anionic polymerization progressing between oligomers.

Japanese Patent Application Laid-Open No. 5-194711 discloses an epoxy resin in which a curing agent for an epoxy resin and a curing accelerator for an epoxy resin are encapsulated with a polymolecular (phenol) host compound. . Specifically, 2
Curing of epoxy resin by adding several percent of 1-ethyl-4-methylimidazole and 2,2'-methylenebis (4-methyl-6-t-butylphenol) as imidazole to epoxy resin Is described. However, although there is a description that the pot life (one-pack stability) is greatly extended, this is a comparison with cyclodextrin, which is a similar inclusion compound, and is not satisfactory in practical use. Further, there is no description or suggestion about heat stability or low-temperature curing characteristics.

JP-A-5-201902 describes an inclusion compound of a tetrakisphenol and imidazole, but does not specifically state that the compound can be used as a curing agent or a curing accelerator for a resin.

JP-A-60-40125, JP-A-8-1
No. 51429 describes that a salt of imidazoline and a polyhydric phenol is used as a curing agent for an epoxy resin, but it is not a crystalline solid but an inclusion compound, and is practical in terms of one-pack stability and the like. Is not satisfactory. Also, US Pat. No. 3,519,576 describes using a salt of an amine and a polyhydric phenol as an epoxy resin curing agent, but is practically satisfactory in effects such as one-pack stability. It's not cool. No. 4,845,234 describes that a salt of an imidazole and a polyhydric phenol is used as a curing agent for an epoxy resin. However, the liquid is a highly viscous liquid, and is not an inclusion compound. The effect is not practically satisfactory.

Japanese Patent Publication No. 6-9868 discloses that a salt of a tetrakisphenol and an imidazole can be used as a curing agent for an epoxy resin, but there is no specific description.
What is described is a salt of imidazole and a polyhydric phenol, and the generated salt is a highly viscous liquid and is not an inclusion compound. The effect is described as one-pack stability, but is not practically satisfactory. There is no description of heat stability and low-temperature curing characteristics.

[0008] Patent Publication No. 2501154, Japanese Patent Publication No.
No. 74260 describes a resin in which a tetrakisphenol skeleton is introduced into a produced resin using a tetrakisphenol as a curing agent. In this case, the resin having the introduced tetrakisphenol skeleton is characterized, and a large amount of tetrakisphenols as a curing agent is used in an amount of 0.5 to 2 mol per 1 mol of the epoxy group. As for the effect, only one-pack stability is described, and heat stability and low-temperature curing characteristics are not described.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the foregoing circumstances, and has been made under the circumstances.
Improves degradability and significantly improves thermal stability, which is extremely important in controlling the curing reaction when mixed with resin, and extends the pot life (one-pack stability when mixing resin and curing agent, etc.) It is an object of the present invention to provide a resin curing agent and a resin curing accelerator capable of improving the curing properties at low temperatures. At the same time, it is an object of the present invention to provide a resin composition capable of obtaining a stable cured product even under mild conditions, such as promptly and smoothly curing of the resin, regardless of the curing method of the curing agent.

[0010]

Means for Solving the Problems The present invention has made intensive studies to solve the above-mentioned problems, and as a result, by encapsulating a resin curing agent or a resin curing accelerator with a specific tetrakisphenol-based host compound, The present inventors have found that the thermal stability of a curing agent or a curing accelerator for a resin in a resin composition can be improved, the pot life can be greatly extended, and the curing characteristics at low temperatures are improved, and the present invention has been completed. Also, by using a specific tetrakisphenol compound in combination with a compound that reacts with the reactive group of the resin to cure the resin, the resin can be cured quickly and smoothly, and a stable cured product can be obtained even under mild conditions. Was found to be.

That is, the present invention relates to a resin curing agent comprising an inclusion body of a tetrakisphenol compound represented by the general formula [I] and a compound represented by the general formula [II]. A curing accelerator for resins, comprising an inclusion body of a tetrakisphenol compound represented by the formula [I] and a compound represented by the general formula [II].

[0012]

Embedded image

(Where X is (CH_Two)_nAnd n
Is 0, 1, 2, or 3, and R¹~ R⁸ Respectively
Hydrogen atom, lower alkyl group,
Nyl group, halogen atom or lower alkoxy group
You. )

[0014]

Embedded image

(Wherein, R ^{9 to} R ¹² each represent a hydrogen atom, a lower alkyl group, an optionally substituted phenyl group, a heterocyclic group or a lower alkoxy group.
⁹ and R ¹¹ may be each formed a 5-10 membered ring together with the carbon atom and the nitrogen atom to which they are attached, R ¹⁰
And R ¹² together with the nitrogen atom to which they are each attached, may further contain a nitrogen atom in the ring.
May form a membered heterocycle. )

An inclusion of a tetrakisphenol compound represented by the general formula [I] and a compound which reacts with an epoxy group to cure an epoxy resin, and / or a tetrakisphenol represented by the general formula [I] A resin composition comprising an inclusion compound of a compound represented by the general formula [II] and a compound represented by the general formula [II]. Particularly preferably, the content of the inclusion compound is 1 mol of a reactive group of the resin. 0.00 for
It is a resin composition of 1 to 0.1 mol.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION A compound (curing agent) which reacts with a reactive group of a resin used in the present invention to cure the resin,
And a compound (curing accelerator) which accelerates the curing rate of a compound which cures the resin by reacting with a reactive group of the resin is represented by the general formula [I
I].

The curing agent and curing accelerator for the resin used in the present invention are not particularly limited as long as they are compounds represented by the general formula [II], and specific examples thereof include 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5,4,0] undecene-7, isobutylamidine, hexahydrobenzamidine, formamidine, acetamidine, benzamidine, pentaamidine, butaneamidine, Examples include hexane amidine, peptane imidoamide, N, 2 diphenylacetamidine, N-phenyl-N-methylbenzamidine, N-N diphenylacetamidine and the like.

In the present invention, the tetrakisphenol compound which forms an inclusion compound with these compounds (curing agent or curing accelerator) is a compound represented by the general formula [I].

Examples of the substituent represented by R ^{1 to} R ⁸ include a hydroxyl group, a methyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-butyl group.
C1-C6 lower alkyl such as hexyl and cyclohexyl, phenyl optionally substituted by halogen and lower alkyl, halogen such as fluorine, chlorine, bromine and iodine, and methoxy Ethoxy group, t-butoxy group and the like, and C1 -C6 lower alkoxy groups.

The tetrakisphenol used in the present invention is not particularly limited as long as it is a compound represented by the general formula [I], and specific examples thereof include 1,1,2,2-tetrakis (4-hydroxy Phenyl) ethane, 1,1,2,
2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1,
2,2-tetrakis (3-chloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-
Dichloro-4-hydroxyphenyl) ethane, 1,1,
2,2-tetrakis (3-bromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-
Dibromo-4-hydroxyphenyl) ethane, 1,1,
2,2-tetrakis (3-t-butyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3
5-di-t-butyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-4-
(Hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-difluoro-4-hydroxyphenyl)
Ethane, 1,1,2,2-tetrakis (3-methoxy-
4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-methyl-4-) Hydroxyphenyl) ethane, 1,
1,2,2-tetrakis (3-bromo-5-methyl-4
-Hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methoxy-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-t
-Butyl-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-bromo-4-hydroxyphenyl) ethane, 1,1,2,2
2-tetrakis (3-chloro-5-phenyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis [(4-hydroxy-3-phenyl) phenyl] ethane, 1,1,3,3- Tetrakis (4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-methyl-4-hydroxyphenyl) propane, 1,1,
3,3-tetrakis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-chloro-4-hydroxyphenyl) propane,
1,1,3,3-tetrakis (3,5-dichloro-4-
Hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-bromo-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dibromo-
4-hydroxyphenyl) propane, 1,1,3,3-
Tetrakis (3-phenyl-4-hydroxyphenyl)
Propane, 1,1,3,3-tetrakis (3,5-diphenyl-4-hydroxyphenyl) propane, 1,1,
3,3-tetrakis (3-methoxy-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3
5-dimethoxy-4-hydroxyphenyl) propane,
1,1,3,3-tetrakis (3-t-butyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) propane, 1,1,4,4-tetrakis (4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-methyl-4-hydroxyphenyl) butane, 1,
1,4,4-tetrakis (3,5-dimethyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-chloro-4-hydroxyphenyl) butane, 1,
1,4,4-tetrakis (3,5-dichloro-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-methoxy-4-hydroxyphenyl) butane,
1,1,4,4-tetrakis (3,5-dimethoxy-4
-Hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-bromo-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-dibromo-
4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-t-butyl-4-hydroxyphenyl)
Butane, 1,1,4,4-tetrakis (3,5-di-t
-Butyl-4-hydroxyphenyl) butane and the like. These tetrakisphenol compounds may be used alone or in combination of two or more.

The synthesis of an inclusion compound of a compound for curing the resin (curing agent), a compound for accelerating the curing speed of the compound for curing the resin (curing accelerator) and the tetrakisphenol-based compound includes, for example, a curing agent, a curing accelerator, When the agent is a liquid, a tetrakisphenol-based compound is directly added to the liquid to cause a reaction, and when the compound of the curing agent and the curing accelerator is a solid, the compound is reacted in a liquid containing those compounds. In this way, or by causing a solid-phase reaction of the solid compound and the powdered tetrakisphenol-based compound directly, the inclusion compound is produced with high selectivity and high yield. The clathrate compound of the present invention is formed when guest molecules enter crystal lattice vacancies formed by host molecules. Therefore, which compound is easily taken in as a guest is governed by the size, steric shape, polarity, solubility, and the like of the guest molecule. The resulting inclusion compound is a crystalline solid.

Examples of the uncured resin to which the present invention can be applied include known resins such as an epoxy resin, a urethane resin and an acrylic resin, and a resin which is cured by reacting with the compound represented by the general formula [II]. There is no particular limitation. These resins may be used alone or as a mixture of two or more.

According to the present invention, the resin curing agent and the curing accelerator represented by the general formula [II] are used as an inclusion compound with the tetrakisphenol-based compound represented by the general formula [I]. As a curing agent or a curing accelerator for epoxy resin, urethane resin, acrylic resin, silicone resin and the like.

The amount of the clathrate compound to be used may be the same amount as that of a usual curing agent and curing accelerator, and by reacting with the reactive group of the resin, the curing agent molecules are always incorporated into the cured resin. In the case of the addition type curing agent, the clathrate compound is usually used such that the amount of the curing agent included in 1 mol of the reactive group of the resin is about 0.3 to 1.0 mol depending on the properties of the resin required. use. In addition, in the case of a polymerization type curing agent or a photoinitiated type curing agent that causes a polymerization addition reaction between oligomers by acting on a reactive group catalytically without the curing agent molecule being incorporated into the resin, and also used as a curing accelerator In such cases, it is sufficient that the amount of the clathrate compound is not more than 0.2 mol per 1 mol of the reactive group of the resin. Particularly, in the present invention, by using an inclusion compound using a tetrakisphenol-based compound, a small amount is sufficient, and a usage amount of 0.001 to 0.1 mol, or even 0.001 to 0.05 mol may be used. These clathrates can be used alone or in combination of two or more.

When a curing agent for a resin or a curing accelerator for a resin comprising the clathrate compound of the present invention is blended with the above-mentioned uncured resin, the thermal stability which is extremely important in controlling the curing reaction has a problem. Compound in the curing agent and curing accelerator for resin (curing agent before inclusion, represented by general formula [II],
This is significantly improved as compared with the case where only the curing accelerator) is blended. The resin curing agent or resin curing accelerator of the present invention has good moisture resistance during storage and does not undergo decomposition or sublimation. In addition, resin compositions containing these clathrates as curing agents or curing accelerators have excellent thermal properties. The thermal properties of the resin composition include stability at room temperature (one-pack stability), thermal stability during heating from room temperature to a desired curing temperature, and curing temperature.
One property is required. The uncured resin containing the curing agent and the curing accelerator of the present invention is extremely stable at room temperature (good one-pack stability), but cures only by heating to a certain temperature above a certain temperature, and quickly Gives the desired cured product. Also in this case, the curing does not start up to about 80 ° C. and the thermal stability is excellent. However, the generally desired 100-130
Hardening progresses rapidly at around ℃. When a known curing agent / curing accelerator is used, curing gradually starts by heating before the desired curing temperature is reached, which adversely affects the properties of the cured resin. When a known curing agent having relatively excellent thermal stability is used, the curing start temperature is 150 to 18
The temperature is as high as 0 ° C., and it can be said that the composition of the present invention can be cured at a lower temperature than these.

According to the present invention, a tetrakisphenol-based compound forms an inclusion compound having excellent crystal preservability with a resin curing agent and a curing accelerator, and a resin composition using the inclusion compound has extremely low thermal characteristics. As mentioned above, it was found to be excellent. Further, the tetrakisphenol-based compound forming the clathrate compound is a compound that has been known as an addition-type curing agent. However, the present inventors have found that the tetrakisphenol-based compound itself has an excellent catalytic action for curing the resin.

Due to the excellent catalytic action of the resin curing of the tetrakisphenol compound itself, in the resin composition containing the tetrakisphenol compound of the present invention, the curing reaction proceeds quickly and smoothly even under mild conditions, and the resin composition is stable. As a result, the cured properties of the resin composition are significantly improved as compared with the case of curing using only a curing agent.

The temperature at which the clathrate compound of the present invention releases the curing agent and the curing accelerator, which is a guest, is substantially determined by the combination of the guest and the host and the type of resin added. In the clathrate compound of the present invention, by selecting the combination of the guest compound and the host compound so as to release the guest compound at a target temperature, the temperature at which the guest compound is released can be intentionally changed. The release temperature of the guest compound can be controlled by adding a substance that affects the interaction between the guest and the host. Examples of the substance having an influence include organic solvents and substances that form an inclusion compound with a host compound as well as a guest compound that has already been included.

From these facts, when the inclusion compound of the resin curing agent represented by the general formula [II] and the tetrakisphenol-based compound is used as the curing agent for the resin, the curing agent that has been included by heating is reduced. Due to the double effect that the tetrakisphenol compound acts as a catalyst at the same time as the release, a resin composition having a very small amount and extremely excellent thermal properties (one-pack stability, thermal stability, low-temperature curing) can be obtained. It is.

The resin composition of the present invention includes, in addition to those described above,
If necessary, various additives such as a plasticizer, an organic solvent, a reactive diluent, a bulking agent, a filler, a reinforcing agent, a pigment, a flame retardant, a thickener and a release agent can be blended.

The resin curing agent and the resin curing accelerator of the present invention are used for curing resins, for example, resin-based adhesives,
It can be suitably used for applications such as semiconductor encapsulants, laminates for printed wiring boards, varnishes, powder coatings, casting materials, and inks.

[0033]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention.

Example 1 Production of an Inclusion Compound An inclusion compound was produced using various curing agents and curing accelerators and a tetrakisphenol-based host compound, or by the method described above. When the curing agent or the curing accelerator is liquid at room temperature, 1 part by weight of the host compound is added to 10 parts by weight thereof, and the mixture is stirred at 25 ° C. to 100 ° C. for 1 minute to 120 minutes and then left for 1 hour to 48 hours Thus, crystals were precipitated. After the crystals were collected by filtration, they were dried under reduced pressure at room temperature to 120 ° C. to obtain the clathrate compound of the present invention. When the curing agent or the curing accelerator is solid, they are mixed with the host compound at a specific molar ratio, and 1? The inclusion compound of the present invention was obtained by kneading in a kneader at 60 ° C. for 30 minutes. As described above, a method for producing an inclusion compound by directly mixing a curing agent or a curing accelerator with a host compound is described below as “Ne
abbreviated as "at". A curing agent or a curing accelerator is dissolved in any of methanol, ethyl acetate and dichloromethane,
To this, a host compound is added in a ratio of 0.1 mol to equimolar to the curing agent or the curing accelerator, and dissolved or suspended by heating at room temperature to the reflux temperature of the solvent, and stirred and mixed for 1 minute to 120 minutes. After that, the crystals were left at room temperature for 1 to 48 hours to precipitate crystals. After the crystals were collected by filtration, they were dried under reduced pressure at room temperature to 120 ° C. to obtain the clathrate compound of the present invention. Tables 1 and 2 show the production results of the clathrate compounds. All of the clathrate samples obtained in the examples were confirmed to be the target clathrate compounds by IR spectrum, NMR spectrum, thermal analysis (TG / DTA), and powder X-ray diffraction pattern measurements. . The abbreviations in Tables 1 and 2 mean the following curing agent, curing accelerator, and host compound, respectively.

Curing agent and curing accelerator DBN: 1,5-diaza-bicyclo (4,3,0) non-5-ene DBU: 1,8-diaza-bicyclo (5,4,0) undecene-7

Host compound TEP: 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane TEOC: 1,1,2,2-tetrakis (3-methyl-
4-hydroxyphenyl) ethane TDOC: 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

Thermal analysis (TG / DTA) charts of sample numbers 1 to 6 and 8 to 12 in Tables 1 and 2 are shown in FIGS.
1, 15-20. The IR spectra of sample numbers 1, 2, 3, 5, and 8 are illustrated in FIGS. 1H NMR spectra of Sample Nos. 1 and 2 are illustrated in FIGS. The X-ray diffraction patterns of Sample Nos. 1 and 2 are illustrated in FIGS.

Example 2 Measurement of Curing Temperature of Resin Composition (Part 1) 100 parts by weight of base resin (uncured resin) UVR6410 (manufactured by Union Carbide Co., Ltd.) are listed in Table 1 as the curing agent of the present invention. Sample No.3,5,8 curing agent for each DB
U was added so as to be 10 parts by weight. 1 at 25 ° C
After kneading for 0 minutes, one part was sampled, and the resin composition was cured using a differential scanning calorimeter (DSC) at a rate of 10 ° C./min under a nitrogen stream of 30 ml / min. The temperature was measured. The DSC chart of each of the resin compositions is shown in FIGS.

Comparative Example 1 Measurement of Curing Temperature of Resin Composition 10 parts by weight of DBU was added to 100 parts by weight of base resin UVR6410. After kneading at 25 ° C for 10 minutes,
The part was sampled, and the curing temperature of the resin composition was measured using a differential scanning calorimeter (DSC) under a stream of nitrogen at 30 ml / min and at a heating rate of 10 ° C./min. FIG. 24 shows a DSC chart of each of the resin compositions.

Example 3 Measurement of Curing Temperature of Resin Composition (Part 2) The curing agents of Sample Nos. 4, 11, and 12 shown in Table 1, which are the curing agents of the present invention, were used as DBUs in 100 parts by weight of base resin UVR6410. 3 parts by weight were added. 25
After kneading at 10 ° C. for 10 minutes, one part was sampled and the resin composition was measured using a differential scanning calorimeter (DSC) under a nitrogen flow of 30 ml / min at a rate of temperature increase of 10 ° C./min. The curing temperature was measured. The DSC chart of each of the resin compositions is shown in FIGS.

Example 4 Measurement of pot life of resin composition 100 parts by weight of the base resin UVR6410 were used as curing agents of the present invention as curing agents of sample numbers 4, 11 and 12 described in Tables 1 and 2 as DBU. 3 parts by weight were added. After kneading at 25 ° C for 10 minutes and further standing at 25 ° C for 20 minutes, the initial viscosity of the resin composition was measured. Thereafter, the resin composition was allowed to stand at 25 ° C., and the change in viscosity with the passage of time was measured until 210 hours. The viscosity was measured using a B8R rotational viscometer (manufactured by Tokyo Keiki) according to JIS K-6833-1994. The measurement results are shown in Table 3 and FIG.

Comparative Example 2 Measurement of pot life of resin composition 3 parts by weight of DBU were added to 100 parts by weight of base resin UVR6410. Knead at 25 ° C for 10 minutes, and further 25
After standing at 20 ° C. for 20 minutes, the initial viscosity of the resin composition was measured. Thereafter, the resin composition was allowed to stand at 25 ° C., and the change in viscosity with the passage of time was measured until 210 hours. The viscosity was measured in the same manner as in Example 4. The measurement results are shown in Table 3 and FIG.

From Table 3, it can be seen that even when the clathrate compound of the present invention is mixed with a resin, it does not cure at room temperature and is stable.

[0047]

The resin curing agent and the resin curing accelerator of the present invention are obtained by encapsulating the curing agent represented by the general formula [II] and the curing accelerator with a tetrakisphenol-based host compound. Improves sublimability and decomposability of curing accelerator,
In addition, since the curing action of the curing agent and the curing accelerator does not work in a temperature range equal to or lower than the inclusion release temperature, the pot life of the resin composition can be extended when mixed with the resin. In particular, since the reaction in the low temperature range, which is extremely important in controlling the curing reaction, is suppressed, the curing does not proceed below the target temperature, the low viscosity resin state is maintained, and the inclusion is released above the target temperature. Since the curing agent and the curing accelerator become free and exhibit the original curing action, a resin composition having excellent properties, which cannot be obtained with the conventional curing agent and curing accelerator, can be obtained. Since the resin curing agent and the resin curing accelerator included in the present invention have the above-mentioned characteristics, a resin composition having the following excellent characteristics can be obtained. That is, since the pot life is long, it can be stored in a mixed state, and the complicated mixing work at the site of use is eliminated, and the working efficiency is improved. In addition, since a constant resin composition is always obtained, a final product of uniform quality can be secured. In addition, the inclusion compound of the present invention is not affected by mechanical treatment unlike microcapsules because of the binding at the molecular level,
Since it can be pulverized, the release of the curing agent and the curing accelerator is excellent. In addition, the host contact compound of the present invention has the advantage that the curing speed of the curing agent for curing the resin is promoted, the curing completion time of the resin composition can be shortened, and the amount of the conventional curing agent used can be reduced. For curing, for example, resin adhesives, semiconductor encapsulants, laminates for printed wiring boards, varnishes, powder coatings, casting materials, inks and the like. The present invention can be used for a two-pack type thermosetting resin composition in which curing is started by mixing a main agent and an auxiliary agent, such as an epoxy resin, a urethane resin, an acrylic resin, and a silicone resin.

[Brief description of the drawings]

FIG. 1 is a thermal analysis (TG / DTA) chart of an inclusion compound (sample No. 1) shown in Table 1.

FIG. 2 shows the results of the inclusion compound (sample No. 1) shown in Table 1.
1H NMR spectrum chart

FIG. 3 is an IR spectrum chart of the clathrate compound (sample No. 1) shown in Table 1.

FIG. 4 is an X-ray diffraction pattern of an inclusion compound (sample No. 1) shown in Table 1.

FIG. 5 is a thermal analysis (TG / DTA) chart of the clathrate compound (sample No. 2) shown in Table 1.

FIG. 6 shows the results of the inclusion compound (sample No. 2) shown in Table 1.
1H NMR spectrum chart

FIG. 7 is an IR spectrum chart of the clathrate compound (sample No. 2) shown in Table 1.

FIG. 8 is an X-ray diffraction pattern of an inclusion compound (sample No. 2) shown in Table 1.

FIG. 9 is a thermal analysis (TG / DTA) chart of the clathrate compound (sample No. 6) shown in Table 1.

FIG. 10: Inclusion compounds described in Table 1 (Sample No. 9)
Analysis (TG / DTA) chart

FIG. 11: Inclusion compounds shown in Table 1 (sample No. 1)
0) Thermal analysis (TG / DTA) chart

FIG. 12: Inclusion compounds described in Table 1 (Sample No. 3)
IR spectrum chart

FIG. 13: Inclusion compounds shown in Table 1 (Sample No. 5)
IR spectrum chart

FIG. 14: Inclusion compounds described in Table 1 (Sample No. 8)
IR spectrum chart

FIG. 15: Inclusion compounds described in Table 1 (Sample No. 3)
Analysis (TG / DTA) chart

FIG. 16: Inclusion compounds described in Table 1 (Sample No. 5)
Analysis (TG / DTA) chart

FIG. 17: Inclusion compounds described in Table 1 (Sample No. 8)
Analysis (TG / DTA) chart

FIG. 18: Inclusion compounds described in Table 1 (Sample No. 4)
Analysis (TG / DTA) chart

FIG. 19: Inclusion compounds shown in Table 2 (sample No. 1)
Thermal analysis (TG / DTA) chart of 1)

FIG. 20: Inclusion compounds shown in Table 2 (sample No. 1)
2) Thermal analysis (TG / DTA) chart

FIG. 21: Inclusion compounds described in Table 1 (Sample No. 3)
Chart of resin composition to which is added

FIG. 22. Inclusion compounds shown in Table 1 (Sample No. 5)
Chart of resin composition to which is added

FIG. 23: Inclusion compounds described in Table 1 (Sample No. 8)
Chart of resin composition to which is added

FIG. 24 shows the D of the resin composition to which DBU (not included) was added.
SC chart

FIG. 25: Inclusion compounds described in Table 1 (Sample No. 4)
Chart of resin composition to which is added

FIG. 26: Inclusion compounds shown in Table 2 (sample No. 1)
DSC chart of resin composition to which 1) was added

FIG. 27: Inclusion compounds shown in Table 2 (sample No. 1)
DSC chart of resin composition added with 2)

FIG. 28 shows sample Nos. Of Example 3 and Comparative Example 2. 4,1
Pot life (viscosity) measurement results of resin compositions to which 1, 12 and DBU were added

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 257/10 C07C 257/10

Claims (4)

[Claims] 1. A tetrakisphefe represented by the general formula [I]
Encapsulation of a compound represented by the general formula [II]
A resin curing agent comprising a contact body. Embedded image(Wherein X is (CH_Two)_nAnd n is 0, 1, 2
Or 3 and R¹~ R⁸ Represents a hydrogen atom and a lower
Alkyl group, phenyl group which may be substituted, halogen
And a lower atom or a lower alkoxy group. )(Where R⁹~ R¹²Are hydrogen atom and lower alkyl, respectively.
Group, a phenyl group which may be substituted, a heterocyclic group or
Represents a lower alkoxy group. Further, R⁹And R¹¹Each
Together with the carbon and nitrogen atoms to which they are attached
And may form a 5- to 10-membered ring;^TenAnd R¹²Are each
Together with the nitrogen atom to which it is attached
Forms a 5- to 7-membered heterocyclic ring optionally containing a nitrogen atom
May be. ) 2. A curing accelerator for resin comprising an inclusion body of a tetrakisphenol compound represented by the general formula [I] and a compound represented by the general formula [II]. 3. A resin composition comprising at least one clathrate of a tetrakisphenol compound represented by the general formula [I] and a compound represented by the general formula [II]. 4. An inclusion body of a tetrakisphenol compound represented by the general formula [1] and a compound represented by the general formula [II] is used in an amount of 0.001 to 0.1 with respect to 1 mol of a reactive group of the resin.
The resin composition according to claim 3, which is in mole.