JPS5953526A - Latent curing agent for epoxy resin - Google Patents

Abstract

PURPOSE:To provide titled agent of rapid curability at low temperatures having high storage stability at room temperature, comprising an addition reaction product prepared from a multifunctional epoxy compound, phenol (or alcohol) having tertiary amino group, etc. CONSTITUTION:(A) a mltifunctional epoxy compound (e.g.,bisphenol A type epoxy resin), (B) a tertiary amino group-contg. phenol or alcohol (e.g., 2-dimethyl quinoethanol), and, preferably, (C) a polyhydric phenol (e.g., bosphenol A) are subjected to addition reaction to obtain the objective curing agent with a curing temperature of pref. 60-180 deg.C. The amount ratio of the component (A) to (B) is pref. such that the epoxy equivalent of the component (A) is 0.9-1.5 per equivalent of the OH group in te component (B). The interrelation of the amounts between the components (A), (B), and (C) is pref. such that the epoxy equivalent of the component (A) is 0.9-1.5 times the sum of the OH-equivalents of the components (B) and (c) the component (C) being equal to or less than the component (B) in mole number.

Description

[Detailed description of the invention] TECHNICAL FIELD The present invention relates to a furrowing agent for epoxy fat control.

The present invention further relates to a latent curing agent for epoxy resins that exhibits low-temperature, rapid curing properties and excellent storage stability at room temperature.

Epoxy resins can be cured mechanically or electrically using an acid anhydride curing agent or an amine curing agent. Electrical insulating materials, molded products, adhesives, paints, etc., have been extensively praised in order to provide cured products with desirable chemical properties.However,
An epoxy resin composition containing an amine compound has poor storage stability, and an epoxy resin composition containing an acid anhydride 7i11 is not suitable for use at room temperature. On the other hand, it takes one prefecture for hardening, p quotient τ! 1A
1. It has the disadvantage of requiring long heating time.

Therefore, it is widely practiced to shorten the curing time by using a curing accelerator such as a tertiary amine or quaternary ammonium compound q'//Jη) or I' . However, although the addition of a curing accelerator improves curability, it has the drawback of significantly impairing storage stability. Therefore, a so-called latent curing agent is strongly desired, which is stable at relatively low temperatures, does not gel, and quickly converts into yi when heated.

By the way, several latent curing agents have been proposed so far, such as dicyandiamide, dibasic acid dihydrazide, boron trisulfide, gb-amine adduct, guaomince 1 (melamine compound), etc. However, dicyandiamide, di-W dihydrazide, and guanamines can be used to help the body store.
Height greater than υ1. In addition, the boron trifluoride-amine adduct has a high moisture absorption i1, which has a negative impact on the properties of the cured product. Ifk, which has hardening properties and is difficult to cure, very few chemical compounds are known which have less stability.

The Ministry of the Invention intends to develop a 100% storage agent that has low-temperature, fast-curing properties and is stable in shelf life.
As a result of the investigation, we found that (a) the epoxy compound and (b)
Addition products (a) or the above (a) which can be prepared by reacting with phenol or alcohol having a tertiary amine group in the molecule
In addition to the two components (al and (b)), we added (cl) multi-phenolization agent and reacted, and found that the 4ζJ addition compound, which is neglected, is an excellent latent phenol A11 that meets the undesirable purpose. , became a brother of Honjomei.

In particular, (a), (b) (c) from two-component systems (a) and (b)
The three-component system has better properties in terms of preservation and is superior as a latent curing agent.

The latent curing agent related to Kinei Ichiriki will be explained in detail below.

According to the raw material of the latent +yb agent of the present invention and 2, (a) multi-functional epoxy compound is one having two or more epoxy groups in one molecule, for example t'1 Bisphenol A1 Bisphenol F1 Multi-jail phenols such as catechol and resorcinol; β-Oxina 7) Glycidyl ether esters obtained by reacting hydroquine carboxylates such as chlorhydrin, phthalates, polycarbonates such as terephthalic acids (4t et al.) , voricricidyl ester, 4
．． Glycidylamine compounds obtained from 4'-diaminodiphenylmethane, m-aminophenol, etc., as well as epoxidized noholac, epoxidized polyolefin, etc. are applied. (b) A phenol or alcohol that has a tertiary amine group in the molecule, for example, 2-dimethylamineethanol, 1-
Methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-fil-”, -dimethyl-2
-dimethylaminoethanol, 1-(2-hydroxy-
3-phenoxypropyl)-2-methylimidanol,
1-(2-hydroxy-3-phenoxypropyl)-2
-ethyl-4-methylimidanol, no(2-hydroxy-3-butoxyglovir)-2-methylimidazole, 1-(2-hydroxy-3-ptoxyglovir)-2
-ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidacillin, 1-(2-hydyloxy-3-butoxyglopyl)-2-methylimidacillin, 2-(dimethylaminomethyl)phenol, 2,4,6-dolino, (dimethylaminomethyl)phenol, etc. To the ingredients (c)
JJ/, in minutes. Examples of multiple phenols include bisphenol 8, bisphenol F1, and bisphenol S.
1 Hydroquinone, catechol, resorcinol, pyrogallol, phenol novolak 4iiJ fat, etc. The reaction ratio of both components (a) and (b) to produce an addition compound that is a latent biocuring agent is 1. In this case, the softening temperature of the epoxy groups 08 to 25 of the multi-functional epoxy compound, which is component (a), is low, making it difficult to form powder), and this is used as a latent hardening agent. If it is blended with an epoxy resin, sufficient R retention properties cannot be achieved.

゛Also, for the epoxy base rOH group 1 part 1, the egg compounding proboscis with 25-111 is partially three-dimensional and becomes an infusible solid. Those blended with epoxy resins do not exhibit speed-up properties, and suffer from the disadvantage that the cured product becomes non-uniform.

In addition, the gap in producing a curing agent using the three components (a), (b), and (c) is that Xt L(c) is added to the component (b).
It is preferable to mix the ingredients in equal moles or less, and if the component (C) is 1 mole or less? J., there is an entry point that is 111 points lower than Hokain. Furthermore (a5
), (b), (C) The ratio of the three components is (b), (
c) i + ll] component hydroxyl and blood ridge sum xl, (
a) Epoxy groups of 0.8 to 2516 #(%')
141” with 0.9 to 1.54i this summer (a), (b)
Paste similar to two-component thread! The same is preferred.

This is preferable as a pre-grading agent (=J addition is 15iJ convex OH followed by contact with epoxy 1, I
There is one that satisfies the Sekiho gold and has a fall crystallization level of 60 to 180C. Softening temperature is 60r: When the temperature of the kite stored at the temperature exceeds 1 sot: ', the kuni is inferior. 4-, the potential between light 1 and 1 and 1 and 1] is the valley component of (a), (b), and (C) if the equivalence relationship between the ○H group and the epoxy group is satisfied. Tomo people, 2
Compounds above ki) A may be used in combination, and addition compounds having an arbitrary temperature of conversion can be obtained by mixing the middle groups of the compounds of each component and the mixed Wariya. I can do it.

These stimulants are (a), (b) or (a), (
Is one minute each of b) and (c) enough? M, combine, gelatinize with a 3-trowel, then cool and solidify at a temperature of 80 to 150 [IM], crush to 1,1◇y, or use tetrahydrofuran, dioxygen, In a bath medium such as methyl ethyl ketone, LL, % 11 juvenile spiders can be easily converted into samurai 1 by removing all the solid matter.

The existing aggregation h11 of ``Kien 9'' can also be used as a known conversion plJ, such as i: anhydride, diandiamide, hydrazide, guanamines, and melamine blue. One pup was given 7H and 13 (9E
If you use + stool (hi wholesale) and v1゛, it will improve to 0 history or large rlJ without lowering the storage capacity.Applicable to Motomoto Akira's gradual stimulant. Epoxy resin or 211N or more in one molecule
In this way, the four cities of Zhou and other additions are disputed. Ihi month 11 does not impair sufficient grading property, and if it exceeds 40!4λ plate part, it will cause the performance of the cured product to deteriorate.

[Kunifuenshizenii] Seiru Mehishi ζ〃Specifically 6 according to your own example
I'll tell you my brother.

1 liter and 6 cups of the raw materials used in the example are used for synthesis). .

(a,) Epoxy tree 11i-t 1-Epicote 828J (Product name: Shell Chemical (
i:d) Bisphenol A thread epoxy resin Epoxy equivalent weight 185-190 "Epikoat Gaku 834J (Product name: Shell Kagaku (C)
13) Bisphenol A thread Eboxo resin epoxy 1 company 245-260 [Epicoat + 1ooxJ (Product name: Shell Kagaku V
...) Bisphenol A thread epoxy composition 460-480 "Epicron + 5aoJ" (Product name Inuhiki Ink Chemical (Kikki) Bisphenol, 1 thread epoxy 1 fat epoxy, J4!, 170-190 ( 1)) Phenol or alcohol with e and tertiary amino groups 102-(dimethylaminemethyl)phenol PG-MZI-(2-hydroxy-
3-phenoxyproyl)-2-methylimitazolePL)-Eλ4z 1-(2-hydroquine-3-phenoxyproyl)-2-ethyl-4-methylimidazolepo-PZL 1-(2-hydroxyproyl)-2-methylimidazole 37xnoxyglovir)-2-phenylimitabulin D E A K diethylaminoethanol LIM
APA 1-Methyl-2-dimethylaminoethanonyl 11G-MZ 1-(2-hydroxy-3-ptoxyglovir)-2-methylimitazole (C1 polyphenolic compound LIA bisphenol A) iQ Hydroquinone PG Pyrogallol Synthesis Example 1 ．． Synthesis of adduct of DMAE and [Epicor] 828J [Epicor 828J 3344I! ((1,176
weight) and D M A E 9. C17 (0,1 go 11
11) and all the beakers, take a
Mix well and gradually lower the temperature to 4f/4F while stirring. 7OC
There was a sudden reaction to θ21 in the vicinity) ± eeee, and about 1 Luna between 1
When the reaction was completed, the temperature was kept at 00C until the temperature was reached, and a pale yellow solid was observed. If the body temperature of the paper is 100C,
Let's use sample swallow 1.

Synthesis example 2. Synthesis of adduct of PG-λIZ, BA and "Epicote 828"200+x/3-' equipped with reflux condenser and stirring device
IJ 77 Sconi Pa-MZ 11.6 # (0
, 0s pylorus), BA5.7# (0,05 the same), 50 m/f of methyl ethyl ketone as the f6 medium: Added and heated (while pressing, dissolved in 3 oal of methyl ethyl ketone [Epicor) 828J19, r (o, x per w) )* mj doto (30 minutes). 7F? After 21+1 hours, the mixture was heated under reflux for 2 hours with stirring. The solvent methyl ethyl ketone was distilled off under reduced pressure, and the adduct k''4:J was obtained as a pale yellow solid.

The J section of this adduct rl + A + 140U is 9, and the sample size is 13.

Below, the sample number and softening temperature of the latent pressure curing Δ of the present invention, which was synthesized by adding Synthesis Example 2 to Synthesis Example 1, are shown.

Example 1 Curability, storage stability, and glass transition stiffness were evaluated using the blending ratios shown in Table 1.

1. Method for preparing samples for evaluation Each paulownia wood was degassed and mixed at the mixing ratio shown in Table 1 in a vacuum stirring crusher (manufactured by Ishikawa Factory) for 1 hour under Sottx pressure.

2. Evaluation of curability 2-1) The curing initiation temperature (T1) and peak temperature (Tp) were measured by thermal analysis.

Sample Approximately 101 Standard' (No need to buy α-aluminum tube heating rate 5 C/m1n 2-2) Place the sample in the gear open at constant temperature +y and check the result! The tiger was celebrated as ml.

3. Storage: A sample was placed in a thermostat at a constant temperature (3OC), and the number of days until fluidity disappeared was measured.

4. Glass amount 1 bar 11 method 11 degrees (Y of Dr force l of T
Each time, the sound was collected by heating a sample that had been cured for a certain amount of time, and χJ
It will be understood that -L/hi is in a state of being irritating i't1.

Human model example 2 The curing properties and storage stability of yarns using the combination of the inventive curing agent and dibasic acid hydrazide were evaluated. The formulation is shown in the third coating, and the results are shown in Table 4.

Table 3 Epikote ≠ 828' 100 parts by weight Ajihin hydrazide 8ZnO5 Table 4 *2) Hardening 1゛; Tooc, 60 minutes (However, Sump 11/jM2.6.15 is 150C, 60 minutes) Second
The ratio between the coating and the fourth coating is the same as that of the present invention.
Ishikasei/Bajin 11] lkokai, spear 11. It will be said that what is going on is true.

EXAMPLE A combination system of the present invention's aggressive hardening agent 741J and a known latent curing agent was evaluated to have a 117-100% anti-fouling property.

Table 5 shows the results.

Table 5 The results shown in Table 5 indicate that the known latent/group curing agent alone does not cure at all (1 ooc 1 hour), but when used in combination with the latent 1/1: curing firmness of the present invention, it cures at a temperature of 100 t:'. It is clear that the hardenability of UJ is significantly lower than that of the previous hardened steel.

Claims (1)

[Claims] 1. An epoxy resin composition containing an addition compound obtained by reacting (a) a polyfunctional epoxy compound and (b) a phenol or alcohol having a tertiary amino group in the molecule. A wet hardening agent. 2. A term used to refer to a fertilized FF product obtained by reacting (a) a polyfunctional epoxy compound, (b) a phenol or alcohol having a tertiary amino group in the molecule, and (C) a polyhydric phenol compound. Latent curing agent for epoxy resin.