JP2000154359A - Injecting agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a two-pack mixing type, normal temperature curable injection agent having a low viscosity, a proper pot life and good in operability by consisting of A agent containing a specified epoxy resin and B agent containing a heterocyclic diamine or the like. SOLUTION: This injection agent is obtained by including (A) A agent including (i) a bisphenol-type epoxy resin and (ii), if necessary, a reactive diluent at a weight ratio i/ii=(10:1) to (7:3) and (B) a B agent including (iii) a heterocyclic diamine and (iv) polyamide amine at a weight ratio iii/v=(1:4) to (4:1) preferably (3:7) to (7:3). The mixing amount of the component B is preferably 20-80 pts.wt. per 100 pts.wt. component A. The component i is preferably disphenol-A epoxy resin and the component ii is preferably an alkylmonoglycidyl ether, an alkyldiglycidyl ether or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-part mixture type cold-setting epoxy resin-based filler.

[0002]

2. Description of the Related Art Since the Great Hanshin Earthquake, reinforced piers for road bridges and reinforced concrete floor slabs for 25TL have been developed nationwide. As a typical example of these reinforcement methods, an epoxy resin-based filler is injected and filled in the gap between the steel plate and the steel plate fixed with a gap of several millimeters between the existing concrete structure and the concrete structure and the steel plate. And a method of bonding / fixing.

[0003] The epoxy resin-based filler used in the above method has a low viscosity, an appropriate pot life, good workability, excellent curability even at low temperatures, After that, it is required to exhibit excellent adhesive strength and mechanical strength.

[0004] As an example of a curing agent for imparting a low-temperature quick-curing property to such an epoxy resin-based injection agent, for example,
Japanese Patent Application Laid-Open No. 63-63716 discloses that "polystyrene obtained by allowing hydrogen sulfide to act on glycidyl ether derived from a polyhydric alcohol having a viscosity at 25 [deg.] C. of 200 ps or less or glycidylamine derived from an aromatic amine. A low-temperature fast-curing epoxy resin curing agent containing a mercaptan "is disclosed.

However, in the composition using a mercaptan-based curing agent as disclosed in the above disclosure, since the mercaptan-based curing agent is fast-curing, there is a problem that the pot life is shortened and workability is deteriorated. There is a problem that the adhesive strength and the mechanical strength are low.

[0006] A heterocyclic diamine is also used as a curing agent for an epoxy resin. However, in a composition using a heterocyclic diamine-based curing agent alone, the cured product has a large shrinkage and the cured product is fragile. There are problems such as lack of toughness and poor adhesion to various adherends such as concrete skeletons and steel plates.

Further, an aromatic amine is used as a curing agent for an epoxy resin. However, a composition using an aromatic amine-based curing agent alone has a slow rise in curing speed and an adhesive force after curing. And insufficient mechanical strength.

[0008]

SUMMARY OF THE INVENTION In order to solve the above-mentioned conventional problems, the present invention has a low viscosity, an appropriate pot life, good workability, and curing at a low temperature. It is an object of the present invention to provide a two-part mixed type cold-curable epoxy resin-based injectable agent which exhibits excellent adhesiveness and, after curing, exhibits excellent adhesion to various adherends, excellent mechanical strength and flexibility. And

[0009]

The filler according to the first aspect of the present invention (hereinafter referred to as "first invention") contains a bisphenol-type epoxy resin or a bisphenol-type epoxy resin and a reactive diluent. The content ratio between the bisphenol-type epoxy resin and the reactive diluent is the weight ratio of bisphenol-type epoxy resin / reactive diluent =
An agent A having a ratio of 10/0 to 7/3, a heterocyclic diamine and a polyamidoamine, wherein the content ratio of the heterocyclic diamine and the polyamidoamine is, by weight ratio, heterocyclic diamine / polyamidoamine = 1/4 to 4/1 of the B agent.

Further, the invention according to claim 2 (hereinafter referred to as “second
The injection according to the "invention") is characterized in that in the injection according to the first invention, the mixing amount of the agent B is 20 to 80 parts by weight with respect to 100 parts by weight of the agent A.

The bisphenol-type epoxy resin contained as a main component in the agent A of the injection according to the first invention is a bisphenol-type epoxy resin obtained by reacting bisphenol with, for example, epichlorohydrin, having a bisphenol skeleton in the main chain, and A compound having an epoxy group at the terminal and / or side chain.

The above-mentioned bisphenol type epoxy resin is not particularly limited. For example, bisphenol A type epoxy resin obtained by reacting bisphenol A, bisphenol F, bisphenol AD or the like with epichlorohydrin, bisphenol F type epoxy resin, etc. Epoxy resins, bisphenol AD type epoxy resins and hydrogenated products thereof and the like, and are preferably used.
Among them, a bisphenol A type epoxy resin having a good balance between performance and cost is more preferably used.

Specific examples of the bisphenol type epoxy resin are not particularly limited.
Product name "Epicoat 806, 807, 815, 827,
"Epicoat 800 Series" (both manufactured by Yuka Shell Epoxy Co., Ltd.), such as "Epomix R13"
9, R140 "(manufactured by Mitsui Petrochemical Industries, Ltd.) and trade names" Araldite GY-250, GY-260 "(manufactured by Nippon Ciba Geigy Co., Ltd.) and the like are preferably used.

The bisphenol-type epoxy resin may be used alone or in combination of two or more.

The viscosity of the bisphenol-type epoxy resin is not particularly limited.
The pressure is preferably 15 Pa · s (25 ° C.). The viscosity of the bisphenol epoxy resin is 15 Pa · s (25
If the temperature exceeds (° C), the filling and filling of the gap between the adherends may be deteriorated. Force and mechanical strength may be reduced.

The agent A of the filler according to the first invention may contain a reactive diluent in order to adjust the viscosity of the epoxy resin and the physical properties after curing of the filler.

The reactive diluent which may be contained in the agent A is not particularly limited, but examples thereof include alkyl monoglycidyl ether and alkylenediglycidyl ether, which are preferably used.

Specific examples of the reactive diluent are not particularly limited, and for example, a trade name “YED1”
11, 116, 122, 205, 216 "and the like.
Series "(both manufactured by Yuka Shell Epoxy Co., Ltd.) and trade names" Denacol EX-111, EX-121, EX-14
1, EX-146, EX-211, EX-212 "and the like (hereinafter, manufactured by Nagase Kasei Kogyo Co., Ltd.) and the like, and preferably used, but among them, for example, 1,6-hexanediol A difunctional or more reactive diluent such as diglycidyl ether (for example, trade name “SR-16H”, manufactured by Sakamoto Pharmaceutical Co., Ltd.) is more preferably used.

The reactive diluents may be used alone or in combination of two or more.

In the injecting agent A according to the first invention,
It is necessary that the content ratio of the bisphenol-type epoxy resin to the reactive diluent is bisphenol-type epoxy resin / reactive diluent = 10/0 to 7/3 by weight.

If the bisphenol-type epoxy resin / reactive diluent is less than 7/3 by weight, the cured product of the injectant has reduced adhesive strength and mechanical strength.

In the injecting agent A of the first invention, in addition to the bisphenol-type epoxy resin which is an essential component and the reactive diluent which may be contained, it is necessary that the injecting agent A does not impair the achievement of the object of the present invention. Accordingly, such as non-reactive diluents, softeners, plasticizers, surfactants, adhesion promoters, coupling agents, fillers, colorants, stabilizers, antioxidants, ultraviolet absorbers, defoamers, etc. One or more of various additives may be contained.

The method for producing the injectable agent A according to the first aspect of the present invention is not particularly limited. For example, a bisphenol type epoxy, which is an essential component, may be prepared using a conventionally known stirring mixer such as a universal mixer or a kneader. By uniformly stirring and mixing a predetermined amount of the resin, a predetermined amount of the reactive diluent that may be contained, and one or more predetermined amounts of the various additives to be contained as necessary, Can be obtained.

The agent B of the injecting agent according to the first invention contains a heterocyclic diamine and a polyamidoamine, and the content ratio of the heterocyclic diamine and the polyamidoamine is expressed by a weight ratio of the heterocyclic diamine / polyamidoamine. = 1/4 ~
4/1.

The heterocyclic diamine contained in the above-mentioned agent B is mainly contained to impart excellent mechanical strength to the cured product of the injection, and the polyamidoamine contained in the above agent B is It is mainly contained to suppress the brittleness of the cured product of the injection agent and to impart excellent flexibility to the cured product.

The above-mentioned heterocyclic diamine is not particularly limited.
X-3S, LX-3W, N001, N002, RD1 "
"Epomate" series (both manufactured by Yuka Shell Epoxy Co., Ltd.) and the like are preferably used.

The above heterocyclic diamines may be used alone or in combination of two or more.

The polyamidoamine contained in the agent B is a reaction product of a carboxylic acid of a synthetic or natural fatty acid such as dimer acid and an ethylene amine such as polyethylene polyamine. Various products can be obtained depending on the reaction conditions and the like.

Specific examples of the above polyamidoamine include:
Although not particularly limited, for example, "Lacamide" series such as trade names "Lacamide EA-230, TD-950" (all manufactured by Dainippon Ink and Chemicals, Inc.),
Product name “TOMIDE 235A, 235R, 241, 24
5, 2461 ”and the like, and“ Amamide 375A, 4 ”
"Anchomide" series such as "00, 506"
ACI Japan Limited), trade name "ACR Hardener H4510" (Asahi Denka Kogyo) and the like.
It is preferably used.

The polyamidoamines may be used alone or in combination of two or more.

In the B agent of the injection according to the first invention,
It is necessary that the content ratio of the heterocyclic diamine and the polyamidoamine is, by weight ratio, heterocyclic diamine / polyamidoamine = 1/4 to 4/1, preferably 3/7 to 7/3. is there.

When the weight ratio of the above-mentioned heterocyclic diamine / polyamidoamine is less than 1/4, the adhesive strength and mechanical strength of the cured product of the injecting agent become low, and conversely,
When the weight ratio of the polyamidoamine exceeds 4/1, the pot life of the injection agent becomes short, and the workability deteriorates.

In the injecting agent B according to the first invention, in addition to the essential components, the heterocyclic diamine and the polyamidoamine, the heterocyclic diamine and the polyamidoamine may be used, if necessary, as long as the achievement of the object of the present invention is not hindered. Other than curing agents, curing accelerators, softeners, plasticizers, surfactants, adhesion promoters, coupling agents, fillers, coloring agents, stabilizers, antioxidants, ultraviolet absorbers, defoamers, etc. One or more of various additives may be contained.

The method for producing the injectable agent B according to the first invention is not particularly limited. For example, a heterocyclic diamine, which is an essential component, may be prepared by using a conventionally known stirring mixer such as a universal mixer or a kneader. A predetermined amount of the polyamidoamine, which is also an essential component, and a predetermined amount of one or more of the above-mentioned various additives to be contained, if necessary, by uniformly stirring and mixing, thereby obtaining the desired B agent. Can be obtained.

In the injection according to the first invention, the agent A and the agent B
The mixing ratio with the agent is not particularly limited.
It is preferable that the mixing amount of the agent B is 20 to 80 parts by weight based on 100 parts by weight of the agent.

If the mixing amount of the agent B is less than 20 parts by weight with respect to 100 parts by weight of the agent A, the injection agent may not be sufficiently cured. Conversely, the mixing amount of the agent B may be 80 parts by weight based on 100 parts by weight of the agent A. If the amount exceeds the limit, the excess B agent (curing agent) acts as a plasticizer, and the adhesive strength, mechanical strength, and the like of the cured product of the injection material may decrease.

The method of using the injecting agent according to the first invention is not special. A predetermined amount of the agent A and a predetermined amount of the agent B are charged into a conventionally known stirring mixer, and the mixture is uniformly stirred and mixed. For example, an injection pump may be used to inject and fill the gap to be injected in the adherend. In this case, since the mixture of the agent A and the agent B has a limited pot life, it is preferable to quickly inject and fill the mixture during the pot life, and in particular, the mixing amount of the agent A and the agent B at one time. Since the pot life becomes shorter as the amount becomes larger, it is preferable to inject and fill as soon as possible. In addition, air bubbles are apt to be mixed into the injection agent during mixing operation and injection operation, and as a result, the adhesive strength and mechanical strength of the cured product are likely to be reduced. It is preferred to take.

Next, the injection according to the second invention is characterized in that in the injection according to the first invention described above, the mixing amount of the agent B is 20 to 80 parts by weight with respect to 100 parts by weight of the agent A. 30 to 70 parts by weight.

When the mixing amount of the agent B is less than 20 parts by weight with respect to 100 parts by weight of the agent A, the heterocyclic diamine and the polyamidoamine are equivalent to the equivalent of the bisphenol type epoxy resin or the equivalent of the bisphenol type epoxy resin and the reactive diluent. Is insufficient, and the curing of the injection does not proceed sufficiently, so that the desired adhesive strength, mechanical strength and the like cannot be obtained.

On the other hand, when the mixing amount of the agent B exceeds 80 parts by weight with respect to 100 parts by weight of the agent A, the heterocyclic diamine and the polyamidoamine are equivalent to the equivalent of the bisphenol type epoxy resin or the equivalent of the bisphenol type epoxy resin and the reactive diluent. Is excessive, the excess B agent acts as a plasticizer, and the adhesive strength, mechanical strength, and the like of the cured product of the injection agent are rather reduced.

The first invention and the second invention (hereinafter referred to as "the present invention")
) May be used as an adhesive, a lining agent, a coating agent and the like, as well as an injectable agent.

[0042]

The injection according to the present invention is composed of the agent A having a specific composition and the agent B having a specific composition, and the mixing ratio of the agent A and the agent B is specified so as to be in a specific range. So
It has low viscosity, suitable pot life, good workability, and excellent curability at low temperatures.

Further, since the agent B of the injection agent according to the present invention contains a specific amount of a heterocyclic diamine and a specific amount of a polyamidoamine, the injection agent after curing has excellent adhesion to various adherends. And excellent mechanical strength and flexibility.

[0044]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Examples 1 to 5 and Comparative Examples 1 to 5 assume injections for spring, summer and autumn, and Examples 6 to 10 and Comparative Examples 6 to 10 assume injections for winter. is there. Further, “parts” in the examples means “parts by weight”.

(Example 1)

(1) Production of Injectant Bisphenol A as bisphenol type epoxy resin
85 parts of epoxy resin (trade name “Epicoat 828”, manufactured by Yuka Shell Epoxy) and 1,6 as reactive diluent
-Hexanediol diglycidyl ether (trade name "S
R-16H "(manufactured by Sakamoto Pharmaceutical Co., Ltd.) and 15 parts thereof were uniformly stirred and mixed by a universal mixer to obtain Agent A as an injection.

15 parts of "Epomate LX-3S" (manufactured by Yuka Shell Epoxy) as a heterocyclic diamine and "Lacamide EA-" as a polyamideamine
And 230 parts (manufactured by Dainippon Ink and Chemicals, Inc.) were uniformly stirred and mixed with a universal mixer to obtain an injecting agent B.

(2) Evaluation The performance (viscosity, pot life,
Compressive strength, tensile shear adhesive strength, and Charpy impact strength) were evaluated by the following methods. The results were as shown in Table 1. In addition, as the evaluation standard, “Epoxy resin quality confirmation test standard value” shown in Table 4 was applied in conformity with “Repair epoxy resin construction standard” of the Metropolitan Expressway Public Corporation shown in Table 3.

Viscosity: After mixing the A agent and the B agent uniformly at a mixing ratio of 2/1 (weight ratio), the viscosity was immediately measured with a BH-type rotational viscometer, and the viscosity was evaluated according to the following criteria. [Criteria] ◎ ‥‥ 3000 cps or less ○ ‥‥ 3000-5000 cps × ｐｓ5000 cps or more

Pot life: After uniformly mixing agent A and agent B at a mixing ratio of 2/1 (weight ratio), the temperature that changes with time is measured, and a time-temperature curve (curing heat generation curve) is obtained. Was. In this curve, the time required for the rapid rise of the exothermic temperature to start was determined, and the working time (min) was defined as 70% of the time. However, in the case where the time until the rapid rise of the heat generation temperature is not clear, the pot life was defined as 50% of the time until the maximum heat generation temperature was reached.

Compressive strength: Agent A and Agent B were uniformly mixed at a mixing ratio of 2/1 (weight ratio), and then JIS K-69.
Test specimens were prepared in accordance with 11 "General Test Methods for Thermosetting Plastics", and the compressive strength (kgf / cm ² ) was measured. However, the shape of the test piece was a cube having a side of 20 ± 0.5 mm.

Tensile shear adhesive strength: 2/1 of agent A and agent B
(Weight ratio), and then uniformly mixed according to JIS K
-6850 "Testing method for tensile shearing adhesive strength of adhesive"
A test piece was prepared in accordance with
gf / cm ² ). However, the test piece is JIS G
Cold-rolled steel sheet (thickness 1.6)
mm, width 25 ± 0.5mm, length 125 ± 0.5mm)
The two sheets were manufactured by bonding both ends to a bonding length of 12.5 ± 0.5 mm.

Charpy impact strength: 2 parts of agent A and agent B
After mixing uniformly at a mixing ratio of 1 (weight ratio), JIS
A test piece was prepared according to K-6911, and the Charpy impact strength (kgf · cm / cm ² ) was measured.

(Examples 2 to 5) and (Comparative Examples 1 to 3) Injections were obtained in the same manner as in Example 1 except that the compositions of Agent A and Agent B were as shown in Table 1.

Comparative Example 4 Example 1 was repeated except that the composition of the agent B was only 50 parts of a heterocyclic diamine (trade name “Epomate N001”, manufactured by Yuka Shell Epoxy Co., Ltd.) and did not contain polyamidoamine. In the same manner as described above, an injection was obtained.

Comparative Example 5 Except that the composition of the agent B was only 50 parts of an aromatic modified amine (trade name "Ancamine LOS", manufactured by ACI Japan), and no heterocyclic diamine and polyamidoamine were contained. An injection was obtained in the same manner as in Example 1.

Performance (viscosity, pot life, compressive strength, tensile shear adhesive strength, Charpy impact strength) of the nine types of injectants obtained in Examples 2 to 5 and Comparative Examples 1 to 5
Was evaluated in the same manner as in Example 1. The results were as shown in Table 1.

[0058]

[Table 1]

As is clear from Table 1, the workability of the injections of Examples 1 to 5 according to the present invention was good because the viscosity was low and the pot life was appropriate. The cured product was excellent in all of compressive strength, tensile shear adhesive strength and Charpy impact strength, and exhibited an excellent balance of physical properties.

On the other hand, the content ratio of the bisphenol type epoxy resin to the reactive diluent in the agent A was 7/3.
The injection agent of Comparative Example 1, which was less than (weight ratio), was low in all of the compression strength, tensile shear strength and Charpy impact strength of the cured product.

The injection of Comparative Example 2 in which the content ratio of the heterocyclic diamine to the polyamidoamine in the agent B exceeded 4/1 (weight ratio) was short in pot life and poor in workability. . Conversely, the injection of Comparative Example 3, in which the content ratio between the heterocyclic diamine and the polyamidoamine in the B agent was less than 1/4 (weight ratio), was the compression strength, tensile shear adhesive strength and Charpy impact strength of the cured product. Both were low.

Further, the injecting agent of Comparative Example 4 in which only the heterocyclic diamine was contained in the B agent and no polyamidoamine was contained, and the heterocyclic diamine and the polyamidoamine were not contained in the B agent, All of the injections of Comparative Example 5 containing only the modified amine had a low compression strength and a low Charpy impact strength of the cured product, and a slightly low tensile shear adhesive strength.

(Example 6) 85 parts of "Epicoat 828" as a bisphenol type epoxy resin and 15 parts of "SR-16H" as a reactive diluent were uniformly stirred and mixed with a universal mixer, and the agent A of the injection was mixed. Obtained. Also, 15 parts of trade name "Epomate LX-3W" (manufactured by Yuka Shell Epoxy) as a heterocyclic diamine and 35 parts of "Lacamide TD-950" (manufactured by Dainippon Ink and Chemicals, Inc.) as a polyamidoamine are versatile. The mixture was uniformly stirred and mixed with a mixer to obtain an injectable agent B.

(Examples 7 to 10) and (Comparative Examples 6 to 8) Injections were obtained in the same manner as in Example 6, except that the composition of Agents A and B was as shown in Table 2.

(Comparative Example 9) The composition of the agent B was only 50 parts of mercaptan tertiary amine (trade name "Capcure WR6", manufactured by Yuka Shell Epoxy Co.), and did not contain a heterocyclic diamine and a polyamidoamine. Except for the above, an injection was obtained in the same manner as in Example 6.

(Comparative Example 10) Except that the composition of the agent B was only 50 parts of an aromatic modified amine (trade name "Ancamine LV", manufactured by ACI Japan Limited), and no heterocyclic diamine and polyamidoamine were contained. Was obtained in the same manner as in Example 6.

The performance (viscosity, pot life, compressive strength, tensile shear adhesive strength, and Charpy impact strength) of the ten types of injectants obtained in Examples 6 to 10 and Comparative Examples 6 to 10 was measured in Example 1. The evaluation was performed in the same manner as in the above case. The results were as shown in Table 2.

[0068]

[Table 2]

As is evident from Table 2, the injectables of Examples 6 to 10 according to the present invention had a low viscosity and an appropriate pot life, so that the workability was good. The cured product was excellent in all of compressive strength, tensile shear strength and Charpy impact strength, and exhibited an excellent balance of physical properties.

On the other hand, the content ratio of the bisphenol-type epoxy resin to the reactive diluent in Agent A was 7/3.
The injection agent of Comparative Example 6, which was less than (weight ratio), had low compressive strength and tensile shear adhesive strength of the cured product.

The injection of Comparative Example 7, in which the content ratio of the heterocyclic diamine to the polyamidoamine in the agent B exceeded 4/1 (weight ratio), had a short pot life and poor workability. . Conversely, the injection of Comparative Example 8 in which the content ratio between the heterocyclic diamine and the polyamidoamine in the B agent was less than 1/4 (weight ratio) had low compressive strength and tensile shear adhesive strength of the cured product.

Further, the injection of Comparative Example 9 in which the heterocyclic diamine and the polyamidoamine were not contained in the B agent but only the mercaptan tertiary amine was contained, the performance (viscosity,
Pot life, compressive strength, tensile shear adhesive strength, Charpy impact strength) were all poor. Further, the injection agent of Comparative Example 10 in which only the aromatic modified amine was contained in the agent B without the heterocyclic diamine or the polyamidoamine, the compression strength and the tensile shear strength of the cured product were low, and the pot life and The Charpy impact strength was also slightly inferior.

[0073]

[Table 3]

[0074]

[Table 4]

[0075]

As described above, the injection according to the present invention has a low viscosity and an appropriate pot life, so that it has good workability and also has excellent curability at low temperatures. After hardening, it exhibits excellent adhesive strength to various adherends, excellent mechanical strength, flexibility, etc., so it can be used for various purposes such as injections for civil engineering, adhesives, lining agents, coating agents, etc. It is preferably used.

Claims (2)

[Claims] 1. A bisphenol-type epoxy resin comprising a bisphenol-type epoxy resin or a bisphenol-type epoxy resin and a reactive diluent, wherein the bisphenol-type epoxy resin and the reactive diluent are contained in a weight ratio of bisphenol-type epoxy resin. A reactive / reactive diluent = 10/0 to 7/3;
A composition comprising a heterocyclic diamine and a polyamidoamine, wherein the content ratio of the heterocyclic diamine and the polyamidoamine is a weight ratio of the heterocyclic diamine / polyamidoamine = 1/4 to 4/1 from the B agent. An injectable characterized by being constituted. 2. The injection according to claim 1, wherein the mixing amount of the agent B is 20 to 80 parts by weight with respect to 100 parts by weight of the agent A.