JPS5825324A - Polybutadiene-modified epoxy resin composition - Google Patents

Abstract

PURPOSE:A resin composition excellent in curability in an underwater or moistened condition and capable of forming cured products excellent in flexibility, comprising an epoxy-containing group-bearing 1,2-polybutadiene mixed with an inorganic filler and a curing agent for epoxy resins which contains an inorganic filler. CONSTITUTION:A base agent obtained by adding an inorganic filler to a 1,2- polybutadiene having at least two epoxy-containing groups as terminals is mixed with a curing agent composition prepared by adding an inorganic filler to a curing agent for epoxy resins. As the 1,2-polybutadienes, those containing bisphenol-derived epoxy groups of formulaeI, II etc., are preferred. As the inorganic filler, mention is made of portland cement, calcium carbonate or the like. As the curing agent, there is particularly preferred modified polyamideamine.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has excellent curability in water or under humid conditions,
The present invention also relates to a polyphtadiene-modified epoxy medium resin composition useful for adhesion, filling, sealing, coating, etc., in which the cured product has good flexibility over a long period of time.

Conventionally, resin compositions for this type of application include:
Epoxy resin of bisphenol Am or FJi ■k, dimer acid-modified edoxy resin as a malleable steel, lI
Minute epoxidized 1.2 polybutadiene, or internally or externally epoxidized 1,4 polybutadiene, as well as reactive or non-reactive diluents, inorganic fillers, plasticizers as viscosity reducing agents.

In addition, in order to improve workability and improve curing properties in water or under humid conditions, the main ingredient is a putty-like KWA prepared by adding a deliquescent substance, such as ment, to the main ingredient, and this epoxy curing agent is used as the main ingredient. It is known that the hardening agent is prepared by mixing the hardening agent into a putty. However, these resin compositions generally have hard physical properties after curing, or even if they are somewhat flexible, they become hard over time5. When used as a seal for a contoured structural frame, it cannot follow the movement, expansion and contraction, vibration, and mechanical effects of the frame, resulting in VS warping and peeling. On the other hand, as a compound having rubber elasticity, silicone resin, urethane tree layer,
Thio-flesh trees and the like are also known, but these have almost no hardening properties under FFL conditions or in water, making them impossible to apply to these unpleasant locations. Ta. Therefore, it has been strongly desired to develop a composition that can be cured in water or under V-II wet conditions and that maintains flexibility for a length of 1 aKM even after curing.

Therefore, the inventors of the present invention have proposed the following methods: partially epoxidized 1.2 polybutadiene, dimer acid-modified epoxy resin, internally or externally epoxidized 1.4 polybutadiene, vinyl-terminated polybutadiene, etc. alone or in combination of two or more, styrene resin,
By conveniently using styrene-butadiene Hiker (B? F - brand name of threat rubber manufactured by Gutdrich-Kenkar and Pritish Zeon) formulations, etc., or various reactive diluents, vulcanized rubber powder, etc. Although many studies have been made to obtain a resin material having the above-mentioned physical properties by selecting various curing agents, and by making each curing agent itself into a polymer, no satisfactory product has been found. However, in the present invention, when 1, 2 butadiene having two or more epoxy-containing groups as terminal groups is used as a base, it has good workability and long-term flexibility.

It has been found that it is possible to obtain a putty-like resin adhesive that has good adhesive properties even under water and under ml conditions and is suitable for various uses such as adhesion, filling, blocking, and coating.

The present invention is based on a curing method using a base material obtained by adding and mixing 1,2 polybutadiene K having two or more epoxy-containing groups as end groups, an inorganic filler, and an inorganic filler added to an epoxy curing agent. The present invention provides a polybutadiene-modified Evo + Shi**mg product consisting of a compounding agent.

To explain this in more detail in J11, the 1.2 polybutadiene preferably has @K and a bisphenol capped epoxy group represented by the following general formula.

C-1° or also, the blending ratio of 2-bodabutadiene in II below in the base agent is 10 to 90%, preferably 60 to 90%. Examples of the inorganic filler include Portland cement, mica powder, calcium carbonate, and silica powder, and 90-J, 0% of the total, preferably 30 to 10% is used. If necessary, add reactive or non-reactive diluents such as butyl glycidyl ether and rudadacidyl ether, anti-sagging agents such as asbestos powder, and pigments such as titanium oxide within 10% of the total amount. do.

The curing agent used in the curing compound may be any general curing agent for epoxy resins that is curable at room temperature, and modified polyandamine is particularly preferred.As for the inorganic filler used therein, The same materials as in - for the main ingredient are used, but
Calcium carbonate is good. The mixing ratio of the curing agent and the inorganic filler in the curing compound is 10 to 5 to 111 parts by weight of the inorganic filler per 100 parts by weight of the curing agent, preferably 40 to 60 parts by weight. The weight mixing ratio of is 1:1 to O,S, preferably 1:1.

The resin binding material according to the present invention is prepared by separately heating and mixing each component of the base resin and curing compound using a kneader, etc., kneading them, and then homogenizing both components before use. −
You can make a precept by combining Kl1 and making it into a putty.

Hereinafter, the details of the zero firing will be explained based on examples, but the present invention is not limited thereto. In addition, in Example 1
All parts represent parts by weight.

Example 1 (Main agent, Noseki II) IPl 1! To 80 parts of 1,2 polybutadiene represented by the formula below, 11 parts of Ibensha, - product name, 8 parts of Portotsun, 8 parts of Doryu Mento, 8 parts of My★ powder, 2 asbestos powder as an anti-sagging agent, and coloring. Acid 4F, f1721 as agent
The mixture was uniformly kneaded in a kneader for about 1 hour while adding 1jk L''C8G to 100''CK'jllllh to form a powder.

(Preparation of curing compound 1.0) Tomide! 15 (Modified polyamide amine, Fuji Kasei Kobosha, - Akira 4) 50 Iku, Voltland 1 Fufu 12% @
, 23.5 parts of calcium carbonate, and 2 parts of asbestos powder as an anti-sagging agent were added, and the mixture was stirred for about 30 minutes in a container while heating to 6G-80°C to obtain hardened compound steel 1.

Example 2 The following formulations were combined in the same manner as in Example 1 to prepare base agent A and curing agent B, respectively. 8 parts mica powder
10 parts asbestos powder (anti-sagging agent)
Bipartite titanium oxide 211
(Curing compound 1.) Modified polyamide amine 5 oil Portland cement ZSS calcium carbonate
Part 23.5 Asbestos end (anti-sagging 114)
) 1511 Example 3 In the same manner as in the previous example, base agent A was prepared using the following formulation.

and curing formulation m, were prepared.

C base agent Mu,) IPII-128 arrow 20 parts mp-133
0 parts lPm-1420 parts Portland cement 10 @ mica powder 10 Iku silica powder
61s titanium dioxide
2 parts asbestos powder (anti-sagging M) 2111
(Curing compounding agent 1.) Modified polyamide aluminum SO11g Portland cement 2511 clay
22LSIm asbeth) 11 powder (anti-sagging agent) LS part% 1.2 polybutadiene similar to EPB-14, Nippon Keitatsusha, product name comparison example L (Main ingredient -1 no II) Ebicor) 1001 (Bisphenolum Otori epoxy #L
Saponification Shell Epoxy Co., Ltd., trade name) 10 parts, Ebiko)
1128 (same as M) 40 copies, Portland Semen)
2@II, mica powder 1511゜calcium carbonate 5
2 parts of asbestos powder and 2 parts of titanium oxide as an anti-sag agent were added to kneader #C, and the mixture was stirred and mixed uniformly for about 1 hour while heating at 80 to 100°C to prepare the main ingredient 1. And so.

(Preparation of hardening compounding agent) Tomide 215 (modified polyamide amine, Fuji Kasei Kogyo Co., Ltd., trade name) SO4, 2s parts of Portland cement,
Calcium vertical acid 23L511. Add 1.5 parts of asbestos powder as an anti-sagging agent to about 60-80'C in a kneader.
The mixture was mixed and stirred for 30 minutes while heating to obtain a hardened blended steel.

Comparative Examples 2 to 5 In the same manner as in the previous example, using the following formulation, the main agent insects, ~
A, and hardened compound steels were prepared, respectively.

(Main ingredient h) Ebiko) 1001 5m! Ebiko~
)828 20 parts Epicote 872
(' 10th part ADEKA FP4000 (2)
10@DO?
5 parts mica powder 15 parts calcium carbonate 5 parts asbestos powder (anti-sagging agent) 2IB Portland Seven Ment
26 parts titanium oxide
211$ (Curing agent number modified Boria Z door ζan So@Portland cement 25g calcium carbonate
2L5g anti-sagging agent 1
．． 5 g (base ingredient-3) Tatsureplay yLxu-4xo (3) 2511
Ebiko) 834 (4) 10 parts Epicoat 1128 101g Ebisuto 8
15 (5) 51m Porto 2nd Dragon Mento no @ Mica 11 end
□oll clay powder*
51111゜Anti-sagging agent
Bipartite titanium oxide 3II (
Hardening compounding agent) Modified polyandamine 50 parts Portland cement WOW calcium carbonate
25 parts anti-sagging agent
5 cities (main agent-,) Epicort 872 25 parts Epicort)
871 ”) 5 g carjoler rlQ (7) 3 part DKFPU-8
(8) 17g calcium carbonate
2os portland cement
20@saponified titanium 2m anti-sagging agent 51i! squid powder
3Ii (hardening compound 44) Modified boriaodoamine So@Portland cement 20 parts Shida Chikara powder
20 parts calcium carbonate
6 parts Anti-sag agent 4 parts
Part Epicote 828 20 parts Epicote 834 10 parts Calcium carbonate
Part 7 portland cement
20@3 parts of titanium oxide (
Curing compounding agent 4-) Modified polyamide amine 5041 Portland cement) 2011A mica powder
10@calcium sulfate
18 parts anti-sagging agent
2 parts Note..., (... Dimer acid-modified epoxy resin, Yuka Shell Epoxy Co., Ltd., trade name 121 Flexible modified epoxy resin, Asahi Denka Co., Ltd., trade name (3) Carboxyl group-containing liquid polyisoprene rubber, Kuraray Co., Ltd. , l Product name (4), (l Bisphenol epoxy 111
111flk-formed Quelle Epoki V Co., Ltd., product name ff) Reactive diluent for paint, Yuka Shell Epoxy Co., Ltd., li product name (shun) Urethane-modified epoxy resin, Asahi Denka Co., Ltd., product name ((branch) Internal epoxidized 1.4 polybutadiene,
Idemitsu Oil Co., Ltd., compounded various main ingredients and curing compounding agents in the proportions shown in the table below, conducted experiments on the resulting resin products, and added up the various characteristic values.The results are shown in the table below.

It is clear from this example that even if a conventional putty-like composition has a low initial hardness and is soft, the hardness increases over time and eventually becomes a hard cured product. The resin composition according to the present invention has excellent properties such as almost no change in hardness even after one hour, long-term K11 flexibility, and high adhesion in water and under humid conditions. has.

Next, application examples of the polybutadiene-modified epoxy resin composition according to the present invention will be described with reference to Figure NK.

Figure 1 shows the case where the resin composition 5 related to Honjitsu@ is injected into the joint 3 of the concrete plate 1.1 of an underground structure and used as a sealant, and the resin composition 5 remains unchanged even after curing. Ir
Because of its flexibility, Gontadat frame 1. Even if I expands and contracts with the passage of time, it can sufficiently withstand it and has the effect of preventing water from entering through the seam 3.

Figure 742 shows oil, gas, and water 4! When screwing the substrate 7 in contact with the screw 9 with the screw 9, a resin composition is added to prevent oil, gas, water, etc. from leaking from the screw hole 11 provided in the substrate 7 and the screw 9. This is an example in which the material 15 is coated from above the screw 9 and used as a sealant, and because it has excellent flexibility, it is particularly effective when the substrate 7 is exposed to vibration or stress. .

Iris 31! ! The resin composition 21 is injected into the joint 11119 of the water pipe 17 made of concrete, iron pipe, etc. and hardened.

This is an example of use as a water-resistant and flexible optical filler.

j141Q is a metal weld 11 (bee) 1m) 23 to prevent oil or gas leakage from the welding 111z*23 table.
In this example, *'ljM product 25 parabolic cloth was filled and cured.
It is particularly effective in applications where there is a temperature difference, such as a transformer.

jlsai is an example in which the area near the sea surface of the support 29 of an offshore structure 210 is coated with this book's MIX Amono 31JIC to form a removable jade film to prevent the support 29 from corrosion due to contact with water and air. .

As mentioned above, 1111N related to the present invention! Since the 11-paraboloid has the above-mentioned excellent properties, it can be widely applied to various uses other than those mentioned above.

[Brief explanation of the drawing]

@IQ to Figure 5 are all theory #451 showing application examples of the resin composition according to the present invention.

Claims (1)

[Claims] 1, 2 having two or more epoxy-containing groups as terminal groups
A base material obtained by adding and heating polybutadiene K and an inorganic filler, and a non-III filler added to an epoxy curing agent.
Bodaptagene modified epoxy tree jjH1 year old product consisting of bm heated curing compound.