JPH03195724A - Flexible epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the title one-pack type composition having excellent storage stability, providing a cured material having excellent flexibility and adhesiveness, comprising an epoxy resin, a ketimine, a modified silicone resin, a catalyst, a silane compound and a specific amount of polyester. CONSTITUTION:(A) An epoxy resin (e.g. bisphenol A type epoxy resin) is blended with (B) a ketimine [e.g. 1,2-ethylenebis(isobenzylideneimine) shown by the formula (R1 to R4 are H, 1-6C alkyl, etc.), (C) a modified silicone resin [e.g. poly(methyldimethoxysilyl ethyl ether)], (D) a catalyst (e.g. dibutyltin oxide) for modified silicone resin, (E) a silane compound and (F) 10-150 pts.wt. based on 100 pts.wt. component A of a polyether (e.g. polyethylene glycol) to give the objective composition.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to - a corrugated flexible epoxy resin composition;
More specifically, the present invention relates to a liquid-type flexible epoxy resin composition that has excellent storage stability and excellent flexibility and adhesive properties in a cured product.

<Conventional technology> Traditionally, epoxy resins have been used for their excellent properties.
It is used in a wide range of fields including adhesives, sealants, paints, cast products, and impregnated materials. However, the cured product is
Because the wood is not very flexible, it often cracks due to vibrations and temperature changes. Therefore, epoxy resin compositions cannot be used as adhesives for composite panels in which members such as concrete and metal, which exhibit different coefficients of thermal expansion, are laminated together.

Therefore, in order to improve this drawback, a technology was developed to combine epoxy resin and liquid chloroprene polymer (Japanese Patent Publication No. 6).
1-36774, etc.) were proposed. However, the epoxy resin composition disclosed in Japanese Patent Publication No. 61-36774 had poor adhesive properties.

Furthermore, conventional epoxy resin compositions are two-component, which means that the base resin and curing agent must be measured and mixed immediately before use, resulting in poor workability and uneven physical properties of the cured product. It had some problems.

<Problems to be Solved by the Invention> The present invention attempts to solve the problems associated with the above-mentioned prior art. The purpose of the present invention is to provide a room temperature-curable, corrugated epoxy resin composition that has excellent properties, adhesive properties, heat resistance, and weather resistance.

Means for Solving the Problems> The present invention comprises an epoxy resin (a), a ketimine represented by formula I (b), a modified silicone resin (c), a catalyst for modified silicone resin (d), a silane compound (e), and Provided is a flexible epoxy resin composition containing polyether (f), characterized in that the polyether (f) is contained in an amount of 10 to 150 parts by weight based on 100 parts by weight of the epoxy resin (a). It is.

R'R' 1 C=N-X-N=C...Bow 1 R2R' (In the formula, RI R2R3 and R4 are hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and X is a carbon Number 2~
6 alkylene group or non-adjacent arylene group having 6 to 12 carbon atoms) The modified silicone resin has the formula ll R1 1... (R20) sn -S i = (in the formula, R
1 is a monovalent hydrocarbon group having 1 to 12 carbon atoms, R2 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 0 to 2). It is preferable to use a silicone resin at the end.

Further, the modified silicone resin is the epoxy resin 1
It is preferably contained in an amount of 10 to 500 parts by weight per 00 parts by weight.

The silane compound is preferably an alkoxysilane derivative having a molecular weight of 2000 or less, such as aminoalkylalkoxysilane, epoxyalkylalkoxysilane, mercaptoalkylalkoxysilane, or a copolymer thereof.

Further, it is preferable that the silane compound is contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the epoxy resin.

The polyether preferably has a weight average molecular weight of 400 or more.

Furthermore, the flexible epoxy resin composition of the present invention contains a dehydrating agent of 0.1 to 100 parts by weight based on 100 parts by weight of the epoxy resin.
It is preferable to include 10 parts by weight.

The present invention will be explained in detail below.

First, the components contained in the flexible epoxy resin composition of the present invention will be explained.

The epoxy resin (a) used in the present invention may be any epoxy resin that is liquid at room temperature.

Examples of the epoxy resin (a) include bisphenol A epoxy resins and bisphenol F epoxy resins obtained by reacting bisphenol A, bisphenol F, etc. with epichlorohydrin, epoxy resins hydrogenated with these, glycidyl Examples include ester-type epoxy resins, novolac-type epoxy resins, urethane-modified epoxy resins with urethane bonds, nitrogen-containing epoxy resins epoxidized with metaxylene diamine or hydantoin, rubber-modified epoxy resins containing polybutadiene or NBR, etc. It is not limited to these.

Moreover, the epoxy resin (a) may be used alone or in combination of two or more types.

As a curing agent for the epoxy resin (a), ketimine (b) represented by the following formula I is used.

RI R3 C=N-X-N=C...bow R2R4 (wherein, RI R2R3 and R4 are hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and X is a group having 2 to 6 carbon atoms)
Ketimine (b), which represents an alkylene group of 6 or a non-adjacent arylene group having 6 to 12 carbon atoms, exists stably in the absence of moisture, but becomes a primary amine with moisture,
Functions as a curing agent for epoxy resin (a). That is,
Ketimine (b) is a latent curing agent. This increases the storage stability of the room temperature curable, one-component flexible epoxy resin composition of the present invention containing components (a) to (f), and also provides good curability during use. Become something.

Such ketimines (b) include 1,2-ethylenebis(isopentylidenimine), 1,2-hexylenebis(isopentylidenimine), t,2-propylenebis(isopentylideneimine), p, p-biphenylenebis(isopentylideneimine), i,2-ethylenebis(isopropylideneimine), 1,3-propylenebis(isopropylideneimine), p-phinidinebis(isopentylideneimine), etc. Illustrated.

Ketimine (b) may be used alone or in combination of two or more.

The amount of ketimine (b) used depends on the period for which the flexible epoxy resin composition is stored, but is generally 1 to 60 parts by weight, preferably 10 parts by weight, based on too many parts by weight of the epoxy resin (a). ~30 parts by weight. If it is less than 1 part by weight, the curing speed will be slow, which is undesirable. On the other hand, if it exceeds 60 parts by weight, the epoxy resin (a) will be more likely to harden during storage, resulting in a decrease in storage stability, which is undesirable.

The modified silicone resin (c) used in the present invention refers to a silicone resin into which a functional group such as an amino group, a phenyl group, or an alkoxy group has been introduced. It is preferable to use a silicone resin having terminal ends.

1 (R' O) sn -S i -...
...II (wherein R1 is a monovalent hydrocarbon group having 1 to 12 carbon atoms, R2 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 0 to 2) More specific Examples include silicone resins having a methyldimethoxysilyl group at the end, and commercially available ones, such as poly(methyldimethoxysilylethyl ether) (M
SP20A (manufactured by Kaneffi Chemical Industry Co., Ltd.) can be used.

These modified silicone resins may be used alone or in combination of two or more.

Use of such a modified silicone resin is important for imparting flexibility to the cured product of the epoxy resin composition.

Furthermore, the modified silicone resin also contributes to improving the storage stability of the epoxy resin composition.

The amount of modified silicone resin used is epoxy resin (a) 1
00 parts by weight, preferably 10 to 500 parts by weight,
More preferably, it is 50 to 200 parts by weight. 10
If it is less than 500 parts by weight, the cured product of the epoxy resin composition will not exhibit sufficient flexibility, while if it exceeds 500 parts by weight,
This is not preferable because the adhesiveness deteriorates.

The modified silicone resin catalyst (d) is a catalyst that cures the above modified silicone resin (c). That is, the modified silicone resin (c) is cured by moisture in the air in the presence of the modified silicone resin catalyst (d).

More specifically, tin compounds such as dibutyltin oxide, metal salts of carboxylic acids such as lead octylate, and amine salts such as dibutylamine-2-ethylhexoate are exemplified. may be used together.

The amount of catalyst (d) for modified silicone resin to be used is - 0 to 100 parts by weight of modified silicone resin (c) to conclude the contract.
．． It is 1 to 10 parts by weight.

The silane compound (e) used in the present invention has the following formula I11
Refers to the so-called silane coupling agent shown in the following, its copolymer, and the reaction product of the coupling agent and the polymer.

R'St (OR')3...
・Tsukasa I! (In the formula, R1 is an alkyl group, R2 is an amino group,
(Organic functional groups such as mercapto group, vinyl group, epoxy group, etc.) Note that the silane compound (e) includes aminoalkylalkoxysilane, epoxyalkylalkoxysilane,
It is preferable to use a mercaptoalkylalkoxysilane or an alkoxysilane derivative which is a copolymer thereof.

More specifically, aminopropyltrimethoxysilane,
Examples include a reaction product of aminopropyltrimethoxysilane and vinyltrimethoxysilane, a reaction product of γ-glycidoxypropyltrimethoxysilane and polysulfide, and commercially available products can be used.

The molecular weight of these silane compounds (e) is preferably 2000 or less. If the molecular weight exceeds 2000, adhesiveness tends to deteriorate, which is not preferable.

The silane compound (e) may be used alone or in combination of two or more.

The amount of these silane compounds (e) used is preferably 0.1 to 50 parts by weight per 100 parts by weight of the epoxy resin (a).
Parts by weight, more preferably 1 to 10 parts by weight. 0
．． If it is less than 1 part by weight, it is not preferable because the adhesive properties will deteriorate. On the other hand, if it exceeds 50 parts by weight, the surrounding moisture will react with the silane compound (e) during use, so the modified silicone resin ( c) is not preferred because it becomes difficult to cure.

Polyether (f) is a compound used as a urethane foam raw material, antistatic agent, emulsifier, etc.
It is a poly(alkylene glycol) ether obtained from olefin oxide. In the present invention, it is a component that imparts flexibility to the cured product of the epoxy resin composition.

More specifically, polyethylene glycol, polypropylene glycol, polybutylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, etc. are exemplified, and two or more types may be used in combination.

Polyether (f) also has a weight average molecular weight of 1
Although those having a weight average molecular weight of about 400 to about 10,000 are known, in the present invention, it is preferable to use one having a weight average molecular weight of 400 or more. Polyether (f
) tends to have higher volatility as its weight average molecular weight decreases. Therefore, during heat aging, the unreacted polyether (f) remaining in the cured product of the epoxy resin composition and having a small molecular weight may volatilize, which may deteriorate the flexibility of the cured product.

The amount of polyether (f) used is 1 epoxy resin (a)
00 parts by weight, 10 to 150 parts by weight, and 20 to 150 parts by weight.
Preferably it is 70 parts by weight. If the amount is less than 10 parts by weight, the cured product of the epoxy resin composition will not exhibit sufficient flexibility, while if it exceeds 150 parts by weight, the adhesiveness will deteriorate.

The flexible epoxy resin composition of the present invention includes epoxy resin (a), ketimine (b), modified silicone resin (c),
Catalyst for modified silicone resin (d), silane compound (e)
and polyether (f), but in addition to this,
Preferably, a dehydrating agent is added.

In the dehydrating agent, when the epoxy resin composition is not used, ketimine (b) or modified silicone resin (c) or silane compound (e) reacts with water, causing the epoxy resin (a) or modified silicone resin (c) to harden. - It is used to suppress the damage and improve the storage stability of the corrugated epoxy resin composition.

Examples of the dehydrating agent include vinyltrimethoxysilane and ethyl orthoformate, and it is preferable to use 0.1 to 10 parts by weight based on too many parts by weight of the epoxy resin (a).

The flexible epoxy resin composition of the present invention may further contain anti-aging agents such as titanium oxide, pigments such as carbon black, fillers such as calcium carbonate, and other additives such as ultraviolet absorbers and plasticizers. Additives may also be included.

The flexible epoxy resin composition of the present invention comprises an epoxy resin (
a) Ketimine (b) Modified silicone resin (c)
, modified silicone resin catalyst (d), silane compound (e
) and polyether (f), and additives such as dehydrating agents,
It is manufactured by mixing using conventional methods and stored in a sealed container.

<Examples> Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

(Example) (i) Production of room temperature curable wave-shaped flexible epoxy resin composition Bisphenol A epoxy resin (
Poly(methyldimethoxysilylethyl ether) (manufactured by Kanebuchi Kagaku Kogyo Co., Ltd., trade name MSP20A) as a modified silicone resin, Polyether A (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name DIOLIO)
00) or polyether B (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name DIOL2000), and calcium carbonate were stirred and mixed at room temperature and under reduced pressure (20 Torr or less) using a mixer for high viscosity. Next, vinyltrimethoxysilane (manufactured by Nippon Unicar Co., Ltd., trade name A171) was used as a dehydrating agent.
and aminopropyltrimethoxysilane (manufactured by Nippon Unicar Co., Ltd., trade name Al100) as a silane compound, and stirred under reduced pressure. Also, as a catalyst for modified silicone resin, a dioctyl phthalate solution of dibutyltin oxide (manufactured by Sankyoki Gosei Co., Ltd.) was added. , trade name No. 918) and ketimine (manufactured by Yuka Shell Epoxy Co., Ltd., trade name H-3) were added in the same manner and stirred under reduced pressure to produce a room temperature curable wave-shaped flexible epoxy resin composition.

(ii) Evaluation The room temperature curable wave-shaped flexible epoxy resin composition obtained in (i) was evaluated as follows, and the results are shown in Table 1.

(1) Tack-free time The epoxy resin composition was applied to a slate board to a thickness of 5 mm, and the tack-free time was measured.

(2) Storage stability The epoxy resin composition was placed in a sealed container and stored at 50°C, opened after 5 days, and its properties were evaluated using the following criteria.

O: The rate of change in viscosity is within 50% of the initial viscosity △: The rate of change in viscosity is 50% to 200% of the initial viscosity ×: The rate of change in viscosity is 200% or more of the initial viscosity. The measurement was conducted at 20°C using a B-type viscometer.

(3) Hardness The epoxy resin composition was applied to a polyethylene board to a thickness of 2 mm, cured (20°C, 60% RH, 14 days), and its JISA hardness was measured according to JIS K 6301. .

(4) Adhesion Based on the tensile adhesion test of JIS A 5758, the epoxy resin composition was applied to two rectangular parallelepiped adherends (50 mm
x50mmx25mm mortar or 50mmx5
0 mm x 5 mm of polycarbonate resin) was applied between the adhering surfaces so that the adhesion area was 50 mm x 12 mm, and the thickness was 12 mm, the two adherends were adhered, and then cured (20 mm).
℃ for 14 days, and then 30℃ for 14 days) to prepare a test specimen.

The test specimen was pulled using a tensile tester, and its adhesion was evaluated based on the following criteria.

○: Destruction of the cured product of the epoxy resin composition ×: Interfacial peeling between the adherend and the cured product of the epoxy resin composition As is clear from Table 1, when the flexible epoxy resin composition of the present invention is used, It has excellent workability and storage stability, and its cured product has excellent flexibility and adhesive properties.

When the modified silicone resin is lacking (Comparative Example 1), the tack-free time is too long, the workability is poor, and the storage stability is also poor. Moreover, the cured product lacks flexibility.

Furthermore, when the epoxy resin is absent (Comparative Example 2), the tack-free time and storage stability are excellent, but the adhesiveness of the cured product is poor.

In the absence of polyether (Comparative Example 3), the cured product lacks flexibility.

On the other hand, when polyether is blended in excess (Comparative Example 4), the cured product lacks adhesiveness.

<Effects of the Invention> The present invention provides a room temperature-curable, corrugated flexible epoxy resin composition that has excellent workability and storage stability, and whose cured product has excellent flexibility, adhesiveness, heat resistance, and weather resistance. things are provided.

Since the flexible epoxy resin composition of the present invention is corrugated, there is no need to measure and mix each of the main resin and the curing agent during use, resulting in a cured product with good work efficiency and stable physical properties. will be obtained.

In addition, the flexible epoxy resin composition of the present invention can bond glass, plastic, metal, painted objects, concrete, etc. without a primer, and its cured product has excellent flexibility, so it can be easily resistant to vibrations and temperature changes. The cured product is less prone to cracking and therefore has excellent durability.

Claims (1)

[Claims] (1) Epoxy resin (a), ketimine represented by formula I (b), modified silicone resin (c), catalyst for modified silicone resin (d), silane compound (e) and polyether ( A flexible epoxy resin composition containing 10 to 150 parts by weight of the polyether (f) based on 100 parts by weight of the epoxy resin (a). ▲There are mathematical formulas, chemical formulas, tables, etc.▼... I (In the formula, R^1, R^2, R^3 and R^4 are hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and X is (represents an alkylene group having 2 to 6 carbon atoms or a non-adjacent arylene group having 6 to 12 carbon atoms) (2) The modified silicone resin has the following formula: , R^1 is a monovalent hydrocarbon group having 1 to 12 carbon atoms,
R^2 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, n is 0 to 2
The flexible epoxy resin composition according to claim 1, wherein the flexible epoxy resin composition is a silicone resin having a hydrolyzable silicon functional group at its terminal end. (3) The modified silicone resin is the epoxy resin 1
The flexible epoxy resin composition according to claim 1 or 2, wherein the flexible epoxy resin composition is contained in an amount of 10 to 500 parts by weight based on 0.00 parts by weight. (4) Any one of claims 1 to 3, wherein the silane compound is an alkoxysilane derivative having a molecular weight of 2000 or less, which is an aminoalkylalkoxysilane, an epoxyalkylalkoxysilane, a mercaptoalkylalkoxysilane, or a copolymer thereof. The flexible epoxy resin composition described in . (5) Claims 1 to 4 wherein the silane compound is contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the epoxy resin.
The flexible epoxy resin composition according to any one of the above. (6) The flexible epoxy resin composition according to any one of claims 1 to 5, wherein the polyether is a polyether having a weight average molecular weight of 400 or more. (7) The flexible epoxy resin composition according to any one of claims 1 to 6, further comprising 0.1 to 10 parts by weight of a dehydrating agent based on 100 parts by weight of the epoxy resin.