JP7004899B2 - Resin composition - Google Patents

Description

The present invention relates to a resin composition suitably applied to a connection portion of a general rotary machine or the like.

Conventionally, there has been known a method of insulatingly fixing a connection portion with a room temperature curable epoxy resin to a portion connecting a lead wire and a lead wire of a rotating machine (Patent Document 1).

As an example of such a room temperature curable epoxy resin, Patent Document 2 is known to use a two-component curable composition composed of an epoxy resin and an amine-based curing agent such as an aliphatic polyamine. ..

That is, this Patent Document 2 describes one or more compounds selected from the group consisting of (A) component: epoxy resin, (B) component: aliphatic polyamine, alicyclic polyamine, and modified products thereof, and (C. ) Ingredients: We have proposed a room temperature curable epoxy resin composition containing a complex of boron halide and an amine compound.

Japanese Unexamined Patent Publication No. H04-317533 JP-A-2015-227415

However, the composition of Patent Document 2 has a drawback that curing at a low temperature is significantly delayed, as pointed out in paragraph 0003 of the same document.

Further, looking at the examples of Patent Document 2, there are the following problems. First, in Examples 18 and 19, the pot life (usable time) is fast in a 23 ° C atmosphere, which is about 10 minutes, but in a summer 35 ° C atmosphere, the pot life becomes even shorter and the product cannot be used. There was a problem. On the other hand, in Examples 5, 15 and 16, it takes 16 hours or more to cure, but there is a problem that it is not preferable in consideration of a realistic curing time (within 15 hours, more preferably within 9 hours). Further, in Examples 20 to 23 of the cited document 2, although the solution is attempted by mixing and stirring the five liquids, there is a problem that the workability is affected and it is not preferable.

In addition, since boron halide is a toxic substance, there is a problem that it is not preferable to use because of strict control and regulation.

An object of the present invention is to realize a curable composition that effectively solves these problems.

The present invention employs the following means in order to solve the above object.

First, in order to obtain realistic curability and workability within a workable range, the composition is composed of a main agent that is liquid at room temperature and a curing agent that is liquid at room temperature, and the curing agent is 2. The seed curing agents are mixed and the curing time at 10 ° C. is less than 9 hours, the gelling time at 10 ° C. is less than 9 hours, and the curing time at 35 ° C. is 30 minutes or more. matter. It is preferable to prepare a curable composition that satisfies the viscosity of 1 Pa · s or less at 20 ° C. immediately after mixing the main agent and the curing agent.

If the initial viscosity is too low, the gelation time tends to be too long, and conversely, if it is too high, the gelation time tends to be short. Therefore, by setting practically acceptable conditions based on the viscosity, it is possible to realistically pursue a curable composition that has an appropriate gelling time and curing time regardless of the air temperature and has good workability. Will be.

Specifically, the curable composition of the present invention is a composition composed of a main agent that is liquid at room temperature and a curing agent that is liquid at room temperature. The curing agent is a mixture of two types of curing agents, and the main agent is , Mitsubishi Chemical jER811, jER801PN, jER802, jER816A, jER819. One of the two types of curing agent is one of modified aliphatic polyamines and polyamide amines, and the other curing agent. The agent is a tertiary amine or a polyamide amine, and the addition rate of the curing agent of 1 is 15.2 to 22.8% by weight, and the addition rate of the other curing agent is 8.2 to 17.6% by weight. It is characterized by being.

Such a curable composition can be particularly effective when used in a joint of a general rotating machine.

According to the present invention described above, a realistic workability that is neither too slow nor too fast is appropriately set from the viewpoint of the tendency of gelation and the tendency of curing regardless of the temperature, and the curable composition corresponding to this is appropriately set. Can be effectively provided.

Hereinafter, an embodiment of the present invention will be described. In addition, the numerical range shown by using "-" in this specification indicates the range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.

<Curable composition>
It is a composition consisting of a main agent that is liquid at room temperature and a curing agent that is liquid at room temperature. The curing agent is a mixture of two types of curing agents.
Curing time at 10 ° C is less than 9 hours,
Gelation time at 10 ° C is less than 9 hours,
Curing time at 35 ° C is 30 minutes or more,
The viscosity at 20 ° C immediately after mixing the main agent and the curing agent is 1 Pa · s or less.
A curable composition satisfying the above conditions.

This allows for an appropriate curing time that is neither too slow nor too fast, regardless of the temperature.

(Gelification time, curing time)
The gelling time and curing time are measured based on "JIS C2105".

(viscosity)
It was measured with a single cylinder rotary viscometer (Vistron manufactured by Shibaura System).

(Main agent)
The main agent is a liquid epoxy resin in which one or more of the bisphenyl A type liquid epoxy resin, the bisphenol F type liquid epoxy resin, and the glycidyl ether epoxy resin are combined.

(Hardener)
Two types of curing agents A and B are mixed and used.
The curing agent A is either a modified aliphatic polyamine or a polyamide amine.

(Denatured aliphatic polyamine)
The modified aliphatic polyamine is a modified product of the aliphatic polyamine, and is a compound in which two or more amino groups are bonded to a carbon atom different from that of the aliphatic polyamine in the modified aliphatic polyamine. Even an amine having an aromatic ring in the molecule can be regarded as an aliphatic amine having an aromatic substituent if the above conditions are satisfied, and falls under the aliphatic polyamine in the present invention. Specific examples of the aliphatic polyamine used in the aliphatic polyamine composition of the present invention include those shown below. Ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, hexamethylenediamine, 2,5-dimethyl-2,5-hexanediamine, 2,2,4-trimethylhexamethylenediamine , Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 4-aminomethyloctamethylenediamine, 3,3'-iminobis (propylamine), 3,3'-methyliminobis (propylamine), bis (3-Aminopropyl) ether, 1,2-bis (3-aminopropyloxy) ethane, mensendiamine, isophoronediamine, bisaminomethylnorbornan, bis (4-aminocyclohexyl) methane, bis (4-amino-3) Methylcyclohexyl) methane, 1,3-diaminocyclohexane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc.

(Polyamide amine)
Polyamide amine: A condensate of dimer acid and polyamine.

The curing agent B is a tertiary amine or a polyamide amine.

(Primary amine)
Examples of tertiary amines include 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, triethylenediamine, triethanolamine, piperidine, N, N-dimethylpiperazine, and N. , N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, N-methyldiethanolamine, N, N-diethylisopropanolamine, NT-butyldiethanolamine, N-ethyldiethanolamine, diaza Examples thereof include bicycloundecene and diazabicyclononen.

In order to determine the range of the amount of each of the two types of curing agents to be added and to have an appropriate curing time even at high temperatures, it is a composition consisting of a main agent that is liquid at room temperature and a curing agent that is liquid at room temperature. As the curing agent, the two types of curing agents are mixed to limit the range of the addition rate of the curing agent A and the addition rate of the curing agent B.

(Addition rate)
The addition rate of the curing agent A is determined as follows.
Addition rate of curing agent A = (weight of curing agent A) / (weight of main agent + weight of curing agent A + weight of curing agent B) × 100

The addition rate of the curing agent B is determined as follows.
Addition rate of curing agent B = (weight of curing agent B) / (weight of main agent + weight of curing agent A + weight of curing agent B) × 100

In order to have an appropriate curing time,
The addition rate of the curing agent A is 15.2 to 22.8% by weight.
If the addition rate of the curing agent B is 8.2 to 17.6% by weight, a constant curing time that is neither too fast nor too slow can be obtained regardless of the temperature. Specifically, it can be as follows.

-The curing time at 10 ° C. can be less than 9 hours.
-The gelation time at 10 ° C. can be less than 9 hours.
-The curing time at 35 ° C can be 30 minutes or more.
-The viscosity of the mixed varnish at 20 ° C. can be reduced to 1 [Pa · s] or less.

Since the curable composition is suitable for use in the joint portion of a general rotating machine from the viewpoint of workability and the like, it is desirable that the curable composition is used in the joint portion of a general rotating machine.

Hereinafter, examples and comparative examples of the present invention will be described with reference to Tables 1 to 3.

[Example 1]
(resin)
As the resin component, jER811 manufactured by Mitsubishi Chemical Corporation, which is the main component of the epoxy resin, was used in this embodiment. It should be noted that Mitsubishi Chemical 's jER801PN, jER802, jER816A, jER819 , etc. can also be used.

(Curing Agent A)
A (1) to A (3) were prepared as the curing agent A.
A (1) is ADEKA hardener EH-6028, A (2) is ADEKA hardener EH-4602, and A (3) is Mitsubishi Chemical jER Cure ST12.

(Hardener B)
B (1) to B (4) were prepared as the curing agent B. B (1) is ADEKA hardener EH-210K, B (2) is ADEKA hardener EH-451N, B (3) is SANHO CHEMICAL tomide 275-FA, and B (4) is Mitsubishi Chemical jER cure 3010. .. The same applies to the following examples and comparative examples.

The main agent, the curing agent A (1) and the curing agent B (1) were mixed in a weight ratio of 100: 23: 23 to obtain a curable composition. The curing time at 10 ° C. (hereinafter referred to as low temperature curing time) is within 9 hours, and the gelling time at 10 ° C. (hereinafter referred to as low temperature gelling time) is within 9 hours and at 35 ° C. The curing time (hereinafter referred to as high temperature curing time) was 61 minutes, and the viscosity at 20 ° C. (hereinafter referred to as viscosity) was 0.7 [Pa · s].

[Example 2]
The main agent, the curing agent A (1) and the curing agent B (3) were mixed in a weight ratio of 100: 25: 25 to obtain a curable composition. The low temperature curing time was within 9 hours, the low temperature gelling time was within 9 hours, the high temperature curing time was 56 minutes, and the viscosity was 1 [Pa · s].

[Example 3]
The main agent, the curing agent A (3) and the curing agent B (1) were mixed in a weight ratio of 100: 22: 22 to obtain a curable composition. The low temperature curing time was within 9 hours, the low temperature gelling time was within 9 hours, the high temperature curing time was 83 minutes, and the viscosity was 0.9 [Pa · s].

[Example 4]
The main agent, the curing agent A (3) and the curing agent B (2) were mixed in a weight ratio of 100: 27: 27 to obtain a curable composition. The low temperature curing time was within 9 hours, the low temperature gelling time was within 9 hours, the high temperature curing time was 100 minutes, and the viscosity was 1 [Pa · s].

[Example 5]
The main agent, the curing agent A (2) and the curing agent B (2) were mixed in a weight ratio of 100: 27: 27 to obtain a curable composition. The low temperature curing time was within 9 hours, the low temperature gelling time was within 9 hours, the high temperature curing time was 75 minutes, and the viscosity was 0.9 [Pa · s].

[Example 6]
The main agent, the curing agent A (2) and the curing agent B (4) were mixed in a weight ratio of 100: 33: 12 to obtain a curable composition. The low temperature curing time was within 9 hours, the low temperature gelling time was within 9 hours, the high temperature curing time was 43 minutes, and the viscosity was 0.9 [Pa · s].

[Comparative Example 1]
The main agent, the curing agent A (1) and the curing agent B (4) were mixed in a weight ratio of 100: 31: 6 to obtain a curable composition. The low temperature curing time was 10 hours or more, the low temperature gelling time was 10 hours or more, the high temperature curing time was 70 minutes, and the viscosity was 0.8 [Pa · s].

[Comparative Example 2]
The main agent, the curing agent A (3) and the curing agent B (3) were mixed in a weight ratio of 100: 25: 30 to obtain a curable composition. The low temperature curing time was within 9 hours, the low temperature gelling time was within 9 hours, the high temperature curing time was 22 minutes, and the viscosity was 1.4 [Pa · s].

[Comparative Example 3]
The main agent, the curing agent A (2), and the curing agent B (1) were mixed in a weight ratio of 100:18:24 to obtain a curable composition. The low temperature curing time was within 9 hours, the low temperature gelling time was within 9 hours, the high temperature curing time was 28 minutes, and the viscosity was 0.7 [Pa · s].

[Comparative Example 4]
The main agent, the curing agent A (3) and the curing agent B (4) were mixed in a weight ratio of 100: 48: 14 to obtain a curable composition. The low temperature curing time was 10 hours or more, the low temperature gelling time was 10 hours or more, the high temperature curing time was 51 minutes, and the viscosity was 1.2 [Pa · s].

[Comparative Example 5]
The main agent, the curing agent A (1) and the curing agent B (2) were mixed in a weight ratio of 100: 33: 10 to obtain a curable composition. The low temperature curing time was 10 hours or more, the low temperature gelling time was 10 hours or more, the high temperature curing time was 110 minutes, and the viscosity was 0.8 [Pa · s].

[Comparative Example 6]
The main agent, the curing agent A (2) and the curing agent B (3) were mixed in a weight ratio of 100: 24: 29 to obtain a curable composition. The low temperature curing time was within 9 hours, the low temperature gelling time was within 9 hours, the high temperature curing time was 26 minutes, and the viscosity was 1.2 [Pa · s].

[Comparative Example 7]
The main agent and the curing agent A (1) were mixed in a weight ratio of 100:45 to obtain a curing composition. The low temperature curing time was 15 hours or more, the low temperature gelling time was 15 hours or more, the high temperature curing time was 1 hour, and the viscosity was 1.4 [Pa · s].

[Comparative Example 8]
The main agent and the curing agent A (2) were mixed at a weight ratio of 100: 30 to obtain a curing composition. The low temperature curing time was 10 hours or more, the low temperature gelling time was 10 hours or more, the high temperature curing time was 2 hours, and the viscosity was 1.9 [Pa · s].

[Comparative Example 9]
The main agent and the curing agent A (3) were mixed in a weight ratio of 100:60 to obtain a curing composition. The low temperature curing time was 15 hours or more, the low temperature gelling time was 15 hours or more, the high temperature curing time was 0.3 hours, and the viscosity was 2.3 [Pa · s].

[Comparative Example 10]
The main agent and the curing agent B (1) were mixed in a weight ratio of 100:40 to obtain a curing composition. The low temperature curing time was 10 hours or more, the low temperature gelling time was 10 hours or more, the high temperature curing time was 0.17 hours, and the viscosity was 1.1 [Pa · s].

[Comparative Example 11]
The main agent and the curing agent B (2) were mixed in a weight ratio of 100:50 to obtain a curing composition. The low temperature curing time was 10 hours or more, the low temperature gelling time was 10 hours or more, the high temperature curing time was 0.17 hours, and the viscosity was 1.2 [Pa · s].

[Comparative Example 12]
The main agent and the curing agent B (3) were mixed in a weight ratio of 100:45 to obtain a curing composition. The low temperature curing time was 10 hours or more, the low temperature gelling time was 10 hours or more, the high temperature curing time was 0.38 hours, and the viscosity was 2.2 [Pa · s].

Table 1
Example

Table 2
Comparative example

Table 3
Comparative example

Claims (3)

It is a composition consisting of a main agent that is liquid at room temperature and a curing agent that is liquid at room temperature. The curing agent is a mixture of two types of curing agents.
The main agent is any of Mitsubishi Chemical's jER811, jER801PN, jER802, jER816A, and jER819 liquid epoxy resins, and one of the two types of curing agent is either a modified aliphatic polyamine or a polyamide amine.
Other curing agents are tertiary amines or polyamide amines,
The addition rate of the curing agent of 1 is 15.2 to 22.8% by weight.
A curable composition, wherein the addition rate of the other curing agent is 8.2 to 17.6% by weight.
However, this excludes the case where the curing agent of 1 is a polyamide amine and the other curing agent is a polyamide amine. It is a composition consisting of a main agent that is liquid at room temperature and a curing agent that is liquid at room temperature. The curing agent is a mixture of two types of curing agents.
The main agent is a liquid epoxy resin of any one of Mitsubishi Chemical's jER811, jER801PN, jER802, jER816A, and jER819, and one of the two types of curing agent is ADEKA Hardener EH-4602.
Another curing agent is ADEKA Hardener EH-451N.
The addition rate of the curing agent of 1 is 15.2 to 22.8% by weight.
A curable composition, wherein the addition rate of the other curing agent is 8.2 to 17.6% by weight. The curable composition according to claim 1 or 2, which is used for a joint portion of a general rotating machine.