JPS631973B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is directed to a polybutadiene-modified epoxy resin composition useful for adhesion, filling, sealing, coating, etc., which has excellent curability in water or under humid conditions, and the cured product has good flexibility over a long period of time. Involved. Conventionally, resin compositions for this type of use include bisphenol A type or F type epoxy resins, dimer acid-modified epoxy resins, partially epoxidized 1,2 polybutadiene, or internal additives as flexibility imparting agents. or external epoxidation 1,4
polybutadiene, as well as reactive or non-reactive diluents, inorganic fillers, plasticizers,
Furthermore, in order to improve workability and hardenability in water or under humid conditions, the main ingredient is a putty made by adding deliquescent substances, cement, etc., and an epoxy curing agent is added to this as well as the main ingredient. It is known that a mixture of the two is used as a curing agent compound. However, these resin compositions generally have hard physical properties after curing, or even if they are initially flexible, they become hard over time, so even though they have high mechanical strength, they are not suitable for use in underground structures or When used as a seal for a concrete structure,
It could not follow the movement, expansion and contraction, vibration, thermal effects, etc. of the building frame, and had drawbacks such as cracking and peeling. On the other hand, silicone resins, urethane resins, thiol resins, etc. are also known as compounds with rubber elasticity, but these all have almost no curability under wet conditions or in water. , it was impossible to apply it to such places. Therefore, it can be cured even in water or under humid conditions;
In addition, there has been a strong desire for a composition that maintains flexibility for a long period of time even after curing. Therefore, the present inventor has developed the following research methods: partially epoxidized 1,2 polybutadiene, dimer acid-modified epoxy resin, internally or externally epoxidized 1,4 polybutadiene, a mixture of two or more of them, such as internally or externally epoxidized 1,4 polybutadiene, vinyl-terminated polybutadiene, styrene resin, styrene butadiene, etc. By using Hiker (trade name of synthetic rubber manufactured by BF Gutdoritsu Chemical Co. and British Zeon Co., Ltd.) compounds, or by adding various reactive diluents, vulcanized rubber powder, plasticizers, etc., various types of curing can be achieved. Although repeated studies have been made to obtain a resin composition having the above-mentioned characteristics by selecting the curing agent and by making each curing agent itself into a polymer, no satisfactory material has been found. However, when 1,2 polybutadiene having two or more epoxy-containing groups as terminal groups is used as a base material in the present invention, it has good workability, long-term flexibility, and can be used in water and in water. It has been found that it is possible to obtain a putty-like resin composition that has good adhesive properties even under humid conditions and is suitable for various uses such as adhesion, filling, sealing, and coating. The present invention is based on a main component obtained by adding and mixing an inorganic filler to 1,2 polybutadiene having two or more epoxy-containing groups as end groups, and a curing agent obtained by adding and mixing an inorganic filler to an epoxy curing agent. The present invention provides a polybutadiene-modified epoxy resin composition comprising a compounding agent. To explain this in more detail, the 1,2 polybutadiene preferably has a bisphenol type epoxy group as shown in the general formula below. or Further, the appropriate blending ratio of the 1,2 polybutadiene in the base agent is 10 to 90%, preferably 60 to 90%. Examples of the inorganic filler include portland cement, mica powder, calcium carbonate, silica powder, etc., and it is used in an amount of 90 to 10%, preferably 30 to 10% of the total. If necessary, a reactive or non-reactive diluent such as butyl glycidyl ether or allyl glycidyl ether, an anti-sagging agent such as asbestos powder, and a pigment such as titanium oxide are appropriately added within 10% of the total amount. The curing agent used in the curing compound may be any curing agent for general epoxy resins that is curable at room temperature, and modified polyamide amine is particularly preferred. The inorganic filler used here may be the same as that for the main ingredient, but Portland cement, calcium carbonate, etc. are particularly preferred. The mixing ratio of the curing agent and the inorganic filler in the curing compound is preferably 10 to 80 parts by weight, preferably 40 to 60 parts by weight, per 100 parts by weight of the curing agent. Further, the weight mixing ratio of the main ingredient and the curing compounding agent is 1:1 to 0.5, preferably 1:1. The resin composition according to the present invention is prepared by separately heating and mixing each component of the base resin and the curing compound using a kneader, etc., kneading them, and then uniformly mixing the two before use. This can be achieved by making it The details of the present invention will be explained below based on Examples, but the present invention is not limited thereto. In the examples, all parts represent parts by weight. Example 1 (Preparation of main agent A ₁ ) EPB13 (1,2 polybutadiene represented by the following formula) 8 parts of Portland cement, 8 parts of mica powder, 2 parts of asbestos powder as an anti-sagging agent, and 2 parts of titanium oxide as a coloring agent were added to 80 parts of Nippon Soda Co., Ltd., and heated to 80-100℃. The mixture was uniformly kneaded in a kneader for about 1 hour to obtain the present drug _A1 . (Preparation of hardening compound B ₁ ) Add 25 parts of Portland cement, 23.5 parts of calcium carbonate, and 2 parts of asbestos powder as an anti-sagging agent to 50 parts of Tomide 215 (modified polyamide amine, Fuji Kasei Kogyo Co., Ltd., trade name), and add 60 parts of asbestos powder as an anti-sagging agent. While heating to -80℃, mix and stir in a container for about 30 minutes to cure the cured compound.
It was set as _B1 . Example 2 The following formulations were mixed in the same manner as in Example 1 to prepare base agent A ₂ and curing formulation B ₂ , respectively. (Main agent A ₂ ) EPB-13 50 parts EPB-14* 20 parts Portland cement 8 parts Mica powder 10 parts Calcium carbonate 8 parts Asbestos powder (anti-sagging agent) 2 parts Titanium oxide 2 parts (hardening compound B ₂ ) Modified polyamide Amine 50 parts Portland cement 25 parts Calcium carbonate 23.5 parts Asbestos powder (anti-sagging agent) 1.5 parts Example 3 In the same manner as in the previous example, base agent A ₃ was prepared using the following formulation.
and curing formulation _B3 was prepared. (Main agent A ₃ ) EPB-12B* 20 parts EPB-13 30 parts EPB-14 20 parts Portland cement 10 parts Mica powder 10 parts Silica powder 6 parts Titanium dioxide 2 parts Asbestos powder (anti-sagging agent) 2 parts (hardening compounding agent) B ₃ ) Modified polyamide amine 50 parts Portland cement 25 parts Clay 23.5 parts Asbestos powder (anti-sagging agent) 1.5 parts〓 1,2 polybutadiene similar to EPB-13,
Nippon Soda Co., Ltd., trade name Comparative Example 1 (Preparation of main agent A ₁ ) Epicote 1001 (bisphenol A type epoxy resin, Yuka Ciel Epoxy Co., Ltd., trade name) 10 parts, Epicote 828 (same as above) 40 parts, Portland cement 26 parts, mica powder 15 parts, calcium carbonate 5 parts
Add 2 parts of asbestos powder and 2 parts of titanium oxide as an anti-sagging agent to a kneader, and stir and mix uniformly for about 1 hour while heating at 80 to 100°C to prepare the main ingredient a _1.
And so. (Preparation of hardening compound b ₁ ) Tomide 215 (modified polyamide amine, Fuji Kasei Kogyo Co., Ltd., trade name) 50 parts, Portland cement
25 parts, 23.5 parts of calcium carbonate, and 1.5 parts of asbestos powder as anti-sagging agent, in a kneader at about 60-80℃.
The mixture was mixed and stirred for 30 minutes while heating to obtain a hardening compound _b1 . Comparative Examples 2 to 5 In the same manner as in the previous example, base ingredients a ₂ to a ₅ and curing ingredients b ₂ to b ₅ were prepared using the following formulations, respectively. (Main agent a ₂ ) Epicote 1001 5 parts Epicote 828 20 parts Epicote 872(1) 10 parts ADEKA FP4000(2) 10 parts DOP 5 parts Mica powder 15 parts Calcium carbonate 5 parts Asbestos powder (anti-sagging agent) 2 parts Portland cement 26 Parts Titanium oxide 2 parts (hardening compound B ₂ ) Modified polyamide amine 50 parts Portland cement 25 parts Calcium carbonate 23.5 parts Anti-sagging agent 1.5 parts (base ingredient A ₃ ) Clareprene LIR-410 (3) 25 parts Epicote 834 (4) 10 parts Epicort 828 10 parts Epicort 815(5) 5 parts Portland cement 30 parts Mica powder 10 parts Clay powder 5 parts Anti-sagging agent 2 parts Titanium oxide 3 parts (curing compound b ₃ ) Modified polyamide amine 50 parts Portland cement 20 parts Calcium carbonate 25 parts Anti-sagging agent 5 parts (base agent _a4 ) Epicote 872 25 parts Epicote 871(6) 5 parts Karjolar F10(7) 3 parts ADKFPU-8(8) 17 parts Calcium carbonate 20 parts Portland cement 20 parts Titanium oxide 2 parts Anti-sagging agent 5 parts Mica powder 3 parts (curing compound b ₄ ) Modified polyamide amine 50 parts Portland cement 20 parts Silica powder 20 parts Calcium carbonate 6 parts Anti-sagging agent 4 parts (base ingredient a ₅ ) Polybutadiene R-45EPI ( 9) 40 parts Epicort 828 20 parts Epicort 834 10 parts Calcium carbonate 7 parts Portland cement 20 parts Titanium oxide 3 parts (curing compound b ₅ ) Modified polyamide amine 50 parts Portland cement 20 parts Mica powder 10 parts Calcium carbonate 18 parts Anti-sagging Agent 2 parts Note (1), (6) Dimer-modified epoxy resin, oil-based shell epoxy resin, trade name (2) Flexible modified epoxy resin, Asahi Denka Co., Ltd., trade name (3) Carboxyl group-containing liquid polyester Isoprene rubber, Kuraray Co., Ltd., product name (4), (5) Bisphenol A epoxy resin, Yuka Ciel Epoxy Co., Ltd., product name (7) Reactive diluent for paints, Yuka Ciel Epoxy Co., Ltd., product name (8) ) Urethane-modified epoxy resin, Asahi Denka Co., Ltd., trade name (9) Internally epoxidized 1,4 polybutadiene, Idemitsu Sekiyu Co., Ltd., trade name Experiments were conducted on the composition and the results of measurements of various characteristic values are shown in the table below.

【table】

[Table] As is clear from this example, in the case of conventional putty-like compositions, even if the initial hardness is low and soft, the hardness increases with 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 over time, long-term flexibility, and high adhesion in water and under humid conditions. have characteristics. Next, application examples of the polybutadiene-modified epoxy resin composition according to the present invention will be described based on the drawings. Figure 1 shows concrete plates 1 and 1 for underground structures, etc.
When the resin composition 5 according to the present invention is injected and filled into the joint 3 and used as a sealant, the resin composition 5 remains flexible even after hardening, so that the concrete frames 1, 1 do not deteriorate over time. Even if it expands and contracts over time,
It is sufficiently resistant to this and has the effect of preventing water from entering through the seam 3. FIG. 2 shows the substrate 7 that comes into contact with oil, gas, water, etc.
When screwing together with the screws 9, in order to prevent oil, gas, water, etc. from leaking from the gap 13 between the screw hole 11 provided in the substrate 7 and the screw hole 9, the resin composition 15 is applied to the screw 9.
This is an example in which the material is coated from above and used as a sealant, and because of its excellent flexibility, it has a remarkable effect, particularly in reducing vibration and bending stress on the substrate 7. FIG. 3 shows a resin composition 21 injected into a joint 19 of a water conduit 17 made of concrete, iron pipe, etc. and hardened.
This is an example of use as a filling sealant that has water resistance and flexibility. Figure 4 shows an example in which the present resin composition 25 is applied and cured on the surface of the welded part 23 in order to prevent oil or gas leakage from the metal welded part (beat part) 23. This is particularly effective when applied to easily accessible areas. FIG. 5 shows an example in which the present resin composition 31 is applied to the support 29 of an offshore structure 27 near the sea surface to form a flexible film to prevent the support 29 from corrosion due to contact with seawater and air. be. As described above, since the resin composition according to the present invention has the above-mentioned excellent properties, it can be widely applied to various uses other than those mentioned above.

[Brief explanation of the drawing]

1 to 5 are explanatory drawings showing application examples of the resin composition according to the present invention.

Claims (1)

[Claims] 1. A base material obtained by adding and mixing an inorganic filler to 1,2 polybutadiene having two or more epoxy-containing groups as end groups, and a curing compound obtained by adding and mixing an inorganic filler to an epoxy curing agent. A polybutadiene-modified epoxy resin composition consisting of.