JPH041220A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin composition improved in room temperature storage stability and the elasticity of a cured product by mixing an epoxy resin with a specified ketimine derivative, a modified silicone resin and a catalyst for this resin. CONSTITUTION:A ketimine (a) of the formula [wherein R1 to R4 are each H, 1-6C alkyl or (alkyl)phenyl; X1 to X3 are each 2-6 C alkylene; and m is 0-1] is reacted with at least 0,5mol, per imino group of component (a), at least one member (b) selected from among styrene oxide, butyl-, allyl-, p-tert-butylphenyl-, p-sec-butylphenyl-, m- or p-cresyl, p-cresyl glycidyl ether, vinylcyclohexane dioxide, etc., under anhydrous conditions to obtain a ketimine derivative (H) in which the imino group of the skeleton of component (a) is reacted with component (b). 10-200 pts.wt. epoxy resin (A) is mixed with 1-100 pts.wt. component B, 100 pts.wt. modified silicone resin (C) and 0.1-10 pts.wt. catalyst (D) for component C.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an epoxy resin composition, and more particularly to a liquid-based epoxy resin composition. It is an object of the present invention to provide a one-component epoxy resin composition which has excellent adhesive strength and whose cured product has excellent elasticity after curing.

[Prior Art] As is well known, epoxy resins have excellent properties, especially high adhesive strength, and are widely used in various fields such as adhesives, paints, casting materials, impregnation materials, and sealants. has been done. However, most of these epoxy resins are two-component systems consisting of a so-called base resin and a hardening agent.If the base resin and hardener are pre-mixed, a curing reaction easily occurs, resulting in a hardening reaction. It has the disadvantage that it cannot be left unused (unused) for a long time after use, and its pot life is extremely short. Furthermore, it has been pointed out that the cured product is generally hard and has poor elasticity, which limits its use.

Various methods are known to prolong pot life, such as using latent hardeners and adding acid or acrylonitrile to amine hardeners, but there are few effective methods and there are still no practical methods. We have not yet reached a satisfactory state. As a method to improve elasticity, for example, methods have been developed in which urethane-modified epoxy resins or epoxy resins are used in combination with liquid acrylonitrile butadiene copolymers or polysulfides, but these are two-component systems; It's not a system thing.

[Problem to be solved by the invention]

Therefore, the problem to be solved by the present invention is to develop a new one-component epoxy resin that has excellent storage stability at room temperature and can provide a cured product with excellent elasticity.

[Means to solve the problem]

(a) Epoxy resin (b) Below - Onboard [However, in the formula, R1, Rz, R3 and R4 are the same or different hydrogens, alkyl groups having 1 to 6 carbon atoms, or having or possessing an alkyl group. phenyl group, Xl, x2 and X,
represent the same or different alkylene groups having 2 to 6 carbon atoms, and m is an integer of 0 to 1], and the imino group in the skeleton is styrene oxide, butyl glycidyl ether. and allyl glycidyl ether, Ptert-butylphenyl glycidyl ether, P-seC-butylphenyl glycidyl ether, m+ p+-cresyl glycidyl ether, P-cresyl glycidyl ether, vinyl cyclohexane dioxide, versatic acid glycidyl ester, cardanol modified glycidyl ether , dimer acid glycidyl ester, 1,6-hexanesiol diglycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether,
Propylene glycol diglycidyl ether, 1,4-
An epoxy resin composition comprising (c) a modified silicone resin reacted with at least one of butanediol diglycidyl ether and neopentyl glycol diglycidyl ether, and (d) a catalyst for the modified silicone resin.

Alternatively, the problem can be solved by forming an epoxy resin composition which further contains (ne) a silane compound in addition to the components (a) to (d) above.

[Operation and structure of the invention] According to the research of the present inventor, each of the components (a) to (d) above, especially the imino group of the ketimine of the general formula (1) represented by the above (b), is It has been found that by using a ketimine derivative obtained by reacting with a specific component, the resulting cured product has excellent storage stability despite being a -liquid system, and the resulting cured product has excellent elasticity. Similarly, it has been found that when the above-mentioned silane compound (e) is used in combination, the adhesive strength is greatly improved. The present invention has been completed based on these new findings.

As the epoxy resin used in the present invention as component (a), a wide range of ordinary epoxy resins can be used, and specific examples include bisphenol A.
, bisphenol A type epoxy resin obtained by reacting bisphenol F, bisphenol AD, etc. with epichlorohydrin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, etc., epoxy resins hydrogenated from these, glycidyl ester type epoxy Examples include a novolanc type epoxy resin, a urethane-modified epoxy resin having a urethane bond, a nitrogen-containing epoxy resin obtained by epoxidizing metaxylene diamine or hydantoin, and a rubber-modified epoxy resin containing polybutadiene or NBR.

Examples of the ketimine represented by the general formula (I) used in the present invention include 2,5.8-triaza-1,8
Nonadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,10-diphenyl-
3,6°9-triaza-2,9-undecadiene, 3.
11-dimethyl-4,7,10-)diaza-3,10-
Tridecadiene, 3゜11-diethyl-4,7,10-
Triaza-3,10-tridecadiene, 2,4,12.
14-tetramethyl-5,8,11-triaza 4.11
-pentadecadiene, 2,4,20.22-tetramethyl-5,12,19-triaza-4,19-trieicosadiene, 2.4,15.17-tetramethyl-5,8
, IL14-tetraaza4,14-octadecadiene can be exemplified as a preferred example. Components to be reacted with this include styrene oxide, butyl glycidyl ether, allyl (aliphatic) glycidyl ether,
Ptert-butylphenyl glycidyl ether, P-
seC~butylphenylglycidyl ether, m+p
+-cresyl glycidyl ether, P-cresyl glycidyl ether, vinyl cyclohexane dioxide, versatic acid glycidyl ester, cardanol modified glycidyl ether, dimer acid glycidyl ester, 1
．． At least one of 6-hexanesiol diglycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 4-butanediol diglycidyl ether, and neopentyl glycol diglycidyl ether, especially styrene. Oxides are preferred. These components to be reacted are as described above - Shipura (1)
It reacts with the imino group in ketimine represented by the formula, but when m in the formula is 1, it may react with either or both of the two imino groups. As the reaction method, any method that allows both components to react can be used, and typical methods are as follows. That is, it is desirable to mix the component in an amount of 0.5 mole or more, preferably 1 mole or more, per imino group in the ketimine. Since ketimine is sensitive to moisture, this reaction is carried out under anhydrous conditions.

There is no particular need for heating, but heating may be performed at 150°C for 1 to 2 hours. The blending ratio is such that at least 50% or more, preferably 80% or more, and particularly preferably 100% of the imino groups of ketimine react. Incidentally, there is no problem even if one of the two components remains unreacted.

The modified silicone resin as component (iii) used in the present invention includes: -Ship stock, 6n (R5O)3--Si (wherein R3 is a monovalent hydrocarbon group having 1 to 12 carbon atoms, R
6 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of O to 2.

Specific examples include poly(methyldimethoxysilyl ether), and commercially available products can be used. Only one type of these polyether polymers may be used, or
You may use a mixture of two or more types.

The modified silicone resin catalyst used in the present invention as component (d) is a catalyst for curing the above-mentioned modified silicone resin, and can be used as long as it has this effect. Specific examples include: Metal organic carboxylates such as tin octylate, silver stearate, iron naphthenate, lead octylate, di-n-butyltin-di-laurate, di-n-butyltin-dilaurate, di-n-butyltin-
Organic tins such as ditterate, alkyl titanates, etc. can be used alone or in combination.

The ratio of each of these components (a) to (d) is 10 to 200, preferably 20 to 100 parts by weight, particularly preferably 35 to 10 parts by weight of component (b) to 100 parts by weight of component (c).
0 parts by weight, component (b) 1 to 100, preferably 2 to 40
The amount of component (d) is 0.1 to 10 parts by weight, preferably 6 parts by weight or less.

The ketimine derivative, which is the component (b), mainly acts as a curing agent for epoxy resins, and in particular, it reacts with the above-mentioned specific components, and since the imino groups that should react with the epoxy resin are gone or have decreased, its storage It greatly contributes to stability. When the amount of the ketimine derivative used does not reach the above-mentioned predetermined amount, the curing speed tends to be slow, and when it exceeds the predetermined amount, the pot life tends to become short.

The modified silicone resin as component (c) is mainly related to imparting elasticity and adhesiveness to the cured product after curing, and is cured by moisture in the air in the presence of a catalyst for the modified silicone resin. If the amount of component (c) used does not reach the above-mentioned predetermined value, the elasticity will be insufficient, and if it exceeds the amount, the adhesiveness will tend to decrease.

In the present invention, it is preferable to further use a dehydrating agent in addition to the components (a) to (d) above. Dehydrating agents are mainly used to prevent ketimine from decomposing with water and reacting with epoxy resins, or to prevent modified silicone resins from reacting with water and hardening during storage. Generally, vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, acrylic silanes such as γ-methacryloxyprolyltrimethoxysilane, acetylacetone, and orthoformic acid esters are widely used. etc. are preferably used, and the amount used is 10% of the modified silicone resin.
The amount is about 1 to 10 parts by weight relative to 0 parts by weight.

In the present invention, a silane compound as component (e) may be used in combination as required. The second (e) component is used mainly for the purpose of improving adhesiveness, and usually 1 to 10 parts by weight of epoxy silane or (and) a reaction product of this with amino silane is used per 100 parts by weight of the epoxy resin.

In the present invention, various other additives that have been conventionally used in this type of field may be used as necessary.
More specifically, anti-aging agents, fillers, colorants, plasticizers, viscosity modifiers, ultraviolet absorbers, etc. can be added.

The one-component epoxy resin composition of the present invention can be prepared by any method as long as it can uniformly mix the dehydrating agent and other additives. After preparation, store it in an airtight container as appropriate.

The composition of the present invention can be widely used in any of the applications for which epoxy resins have traditionally been used, and is particularly suitable for adhesives and sealants, as well as pond bed materials, lining materials, paints, and sealants. It is also effectively used as a retaining material.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

Examples 1 to 6 and Comparative Example 1 Predetermined amounts of each of the predetermined components shown in Table 1 below were blended to prepare a liquid-based epoxy resin composition. All numbers indicate parts by weight. The physical properties of the obtained composition were measured.

The results are also listed in Table 1.

Ketimine-1 A product obtained by heating and reacting 1 mole of 2,4,12,14-tetramethyl-5,8,11-triaza-4,11pentadecadiene and 1 mole of styrene oxide at 150°C for 2 hours.

Ketimine-2 Ketimine-2 is obtained by reacting butyl glycidyl ether instead of styrene oxide in Ketimine-1.

Ketimine-3 Ketimine-3 is obtained by reacting allyl glycidyl ether in place of styrene oxide in Ketimine-1.

Ketimine-4 Ketimine 1 without using any styrene oxide and unreacted.

Manufacturing method example 1 100 parts by weight of modified silicone resin (manufactured by Kanebuchi Chemical Co., Ltd., trade name MS Polymer 2OA), 35 parts by weight of epoxy resin (manufactured by Yuka Shell Epoxy, trade name Epicote 828), 130 parts by weight of calcium carbonate, oxidation 20 parts by weight of titanium are stirred and mixed under reduced pressure. There, ketimine-110 parts by weight,
5 parts by weight of vinyltrimethoxysilane (manufactured by Nippon Unicar, trade name: NUC Silicone A171) as a dehydrating agent, 2 parts by weight of epoxysilane (manufactured by Shin-Etsu Chemicals, trade name: KBM403) as a silane compound, dibutyltin compound (trimethoxysilane) as a catalyst for silicone resin. Manufactured by Kyōkisei, product name Stan N0
918) was added and stirred under reduced pressure to produce a composition of the present invention.

Examples 2 to 6 Products were produced in the same manner as in Example 1, except that the types of ketimines were changed to the corresponding ketimines.

Comparative Example 1 A product was produced in the same manner as in Example 1 except that the type of ketimine was changed to the corresponding ketimine.

However, each characteristic in Table 1 was measured by the following method.

Physical Properties of Cured Product The above composition was cured at 20'C165% to a thickness of 2++o.
Leave in RH atmosphere for 7 and 28 days, JIS K
Tensile strength and elongation were measured using a No. 2 dumbbell according to 6301.

Storage stability The above composition was filled into a cartridge and sealed at 20°C
After leaving for 28 days or 7 days at 50°C for 28 days,
The viscosity of the composition was observed. The criteria for evaluation were as follows.

◎... No change ○... Slightly increased viscosity △... Largely increased viscosity ×... Gelling Examples 7 to 11 Instead of Ketimine-1 used in Example 1, the corresponding ketimine was used. A composition was prepared in the same manner as in Example 1 at the blending ratios shown in Table 2. The properties of each of these compositions were measured in the same manner as in Table 1. The results are also listed in Table 2.

Ketimine-5 to Ketimine-9 used in Table 2 were each produced as follows.

The following compounds were used in place of styrene oxide in ketimine-1, and the other treatments were the same as in the case of ketimine-1.

Ketimine-5...P-ter-butylphenyl glycidyl ether ketimine-6...P-sec-butyl glycidyl ether ketimine-7...m+p+-cresyl glycidyl ether ketimine-8...P-sauce Dylglycidyl ether ketimine-9...Vinyl cyclohexane dioxide Examples 12 to 15 In place of ketimine-1 used in Example 1, corresponding ketimines were used, and examples were prepared at the blending ratios shown in Table 3. A composition was prepared in the same manner as in Example 1. The properties of these compositions were measured in the same manner as in Table 1. The results are shown in Table 3. However, Examples 2 and 13 show cases where the component to be reacted is a difunctional epoxy resin. Also, Example 14
and 15, when m is 1 in the ketimine represented by the general formula (I) used in the present invention (i.e., when there are two imino groups in the general formula), the corresponding two imino groups should be reacted. The case where both components were reacted is shown.

The ketimines used in Table 3 are as follows.

Ketimine-10 and 11 1 and 6 respectively in place of styrene oxide in Ketimine-1
-hexanethiol glycidyl ether (ketimine-1
0) and resorcinol diglycidyl ether (ketimine-11), and otherwise treated in the same manner as ketimine-1.

Ketimine-12 2,4,15,17-tetramethyl-5,8,IL14
1 mole of -tetraaza-4,14-octadecadiene and 2 moles of styrene oxide were reacted by heating at 150° C. for 2 hours.

Ketimine-13 Ketimine-12 was treated in the same manner as Ketimine-12 except that 2 moles of phenyl glycidyl ether were used in place of 2 moles of styrene oxide in Ketimine-12.

Examples 16 to 19 and Comparative Example 2 Compositions were prepared in the same manner as in Example 1 using the corresponding ketimines in place of ketimine-1 used in the examples and using the blending ratios shown in Table 4. . The properties of these compositions were measured in the same manner as in Table 1. The results are shown in Table 4. However, in this example, the amount of the component to be reacted with one imino group in ketimine was varied.

Ketimine used in most cases> Ketimine-1 was treated in the same manner as Ketimine-1 except that the amount of styrene oxide used was changed as shown below.

Ketimine-14... Styrene oxide 0.5 mol Ketimine-15... Styrene oxide 0.8 mol Ketimine-16... Styrene oxide 0.9 mol Ketimine-17... Styrene oxide 1.2 mol Examples 20-25 In Example 1, each composition was prepared by using the blending amounts of various components as shown in Table 5, and otherwise processing in the same manner as in Example 1. However, this example shows examples in which various amounts of ketimine were blended. Properties of these compositions were similarly measured. The results are shown in Table 5.

The adhesive properties of each of the compositions obtained in Examples 1 to 25 above were measured. The results are shown in Table 6.

However, the measurement method is as follows.

Adhesiveness: Apply the above composition uniformly on mortar pieces, slate plates, glass, acrylic plates in an area of 50 x 20 x 2 m, and heat at 20°C.
After being left at 65% R1 for 7 days, the cured composition was peeled off by hand and evaluated. The evaluation criteria were as follows.

○... Cohesive failure of the cured composition ×...
- Items broken at the interface of the adherend Table 6 [Effects of the invention] The composition of the present invention has excellent storage stability at room temperature, and the obtained cured product has excellent elasticity, and also has excellent adhesive properties. It is excellent. Therefore, taking advantage of these characteristics, various fields,
It is particularly effectively used in adhesives, sealants, flooring materials, lining materials, paints, and sealants.

(that's all) -1'

Claims (2)

[Claims] (1) (A) Epoxy resin (B) General formula below ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (I) [However, in the formula, R_1, R_2, R_3 and R_4 are the same or different hydrogens, carbon number 1 ~6 alkyl groups, or phenyl groups with or without alkyl groups, X_1, X
_2 and X_3 are the same or different alkylene groups having 2 to 6 carbon atoms, and m is an integer of 0 to 1], and the imino group in the skeleton is styrene oxide, butyl glycidyl ether,
Allyl glycidyl ether, P-tert-butylphenyl glycidyl ether, P-sec-butylphenyl glycidyl ether, m,p,-cresyl glycidyl ether, P-cresyl glycidyl ether, vinyl cyclohexane dioxide, versatic acid glycidyl ester, cardanol Modified glycidyl ether, dimer acid glycidyl ester, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether and neopentyl glycidyl ether An epoxy resin composition comprising (c) a modified silicone resin reacted with at least one glycidyl ether, and (d) a catalyst for the modified silicone resin. (2) The epoxy resin composition according to claim (1), further comprising (e) a silane compound.