Epoxy crystal soft glue and preparation and application thereof

Abstract

This invention belongs to the field of epoxy resin, specifically disclosing a method for preparing epoxy epoxy resin. The method involves pre-reacting a raw material solution containing a polyetheramine curing agent and diluent A to obtain a curing component B. Component B is then mixed with component A, which contains epoxy resin, and subjected to a curing reaction to obtain the epoxy epoxy resin. The diluent A contains at least a glycidyl ether compound. The pre-reaction temperature is 60–90°C. This invention also includes the epoxy resin prepared by the described method and its applications. The process described in this invention can obtain epoxy epoxy resin with excellent performance without the need for auxiliary agents.

Description

Technical Field

[0001] This invention relates to the field of epoxy crystal adhesive technology, specifically to the field of epoxy crystal soft adhesive technology. Background Technology

[0002] Crystal adhesives mainly include hard crystal adhesives and soft crystal adhesives. For example, Chinese patent document CN110408356A discloses an epoxy polyurethane crystal adhesive formula. Chinese patent document CN109988481A discloses a low-viscosity, fast-setting crystal adhesive. Chinese patent document CN106366719A discloses a mildew-resistant, light-curing crystal adhesive. Existing technologies mainly focus on hard crystal adhesives; soft crystal adhesives are relatively less common.

[0003] Epoxy crystal soft glue is composed of high-purity epoxy resin and a curing agent. It boasts advantages such as being environmentally friendly, having a low odor, being non-toxic, and easy to use. The cured product is crystal clear, water-resistant, and corrosion-resistant. Using crystal soft glue can protect the surfaces of craft ornaments, nameplates, and other items, while also increasing the gloss of the product surface.

[0004] However, most existing crystal soft adhesives use diethylenetriamine and p-hydroxybenzenesulfonic acid as curing agents, and most of them require the addition of toughening agents such as polysulfide rubber, nitrile rubber, and gelatin to increase the toughness of the system. However, the addition of toughening agents increases the cost of crystal adhesives, and diethylenetriamine and p-hydroxybenzenesulfonic acid are prone to yellowing, affecting the transparency of the product. After curing, the product is easy to peel off and has poor adhesion. Summary of the Invention

[0005] In view of this, in order to overcome the shortcomings of the prior art, the purpose of this invention is to provide a method for preparing epoxy crystal soft glue, which aims to provide a crystal soft glue that is non-toughened, low-cost, and also has excellent adhesion and softness.

[0006] The second objective of this invention is to provide an epoxy crystal soft gel prepared by the aforementioned preparation method.

[0007] The third objective of this invention is to provide the application of the aforementioned epoxy crystal soft adhesive in the surface protection of craft ornaments and nameplates.

[0008] The fourth objective of this invention is to provide an object having the crystal soft adhesive protective layer described in this invention.

[0009] To address the problem that the lack of toughening components makes it difficult for crystal resin to meet the quality requirements of soft crystal resin, this invention provides the following improvement solution:

[0010] A method for preparing epoxy crystal soft adhesive involves pre-reacting a raw material solution containing a polyetheramine curing agent and a diluent A to obtain a curing component B, mixing the obtained component B with component A containing epoxy resin, and carrying out a curing reaction to obtain the epoxy crystal soft adhesive.

[0011] The diluent A contains at least a glycidyl ether compound;

[0012] The temperature of the pre-reaction is 60–90℃.

[0013] This invention innovatively pre-reacts the polyetheramine curing agent and diluent A, and further combines the glycidyl ether compound components and the joint control of the pre-reaction temperature to help modify and reorganize the chain structure of the curing agent, lengthen the molecular chain, and increase the toughness of the curing agent. It then further composites and cures the curing agent with component A, thus achieving synergy. This allows for the acquisition of crystal soft glue with better performance even without the need for toughening components.

[0014] In this invention, the polyetheramine curing agent includes one or a mixture of polyetheramine D230, polyetheramine D400, and polyetheramine D2000.

[0015] Preferably, the polyetheramine curing agent includes a mixture of polyetheramine D230 and polyetheramine D400; further, the weight ratio of polyetheramine D230 to polyetheramine D400 is 1:7 to 7.5.

[0016] The research of this invention unexpectedly discovered that the innovative use of this preferred combination of curing agents helps to further synergize with the pre-reaction process described in this invention, and helps to further synergistically improve the performance of the prepared crystal soft glue.

[0017] In this invention, a novel approach is taken to use polyetheramine curing agents and glycidyl ether compounds in combination for pre-reaction. By combining the structures of the two and the pre-reaction method, the chain structure of the curing agent can be modified and reorganized. Thus, epoxy crystal soft glue that meets the requirements for use in crystal soft glue can be obtained without the need for conventional toughening agents.

[0018] In this invention, the diluent A contains at least one of C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, and 1,4-butanediol diglycidyl ether.

[0019] Preferably, the diluent A may also contain benzyl alcohol.

[0020] Preferably, the content of glycidyl ether compounds in diluent A is 20 wt.% or more, more preferably 30-50 wt.%. At these preferred proportions, the properties of the prepared crystal soft gel can be synergistically improved.

[0021] In this invention, the polyetheramine curing agent in the raw material solution comprises 75-95 parts by weight and diluent A comprises 10-30 parts by weight; preferably, the polyetheramine curing agent comprises 80-90 parts by weight and diluent A comprises 10-20 parts by weight; more preferably, the polyetheramine curing agent comprises 80-85 parts by weight and diluent A comprises 15-20 parts by weight.

[0022] In this invention, the solution system before or after the pre-reaction also contains a decolorizing agent A and a UV absorber. For example, the decolorizing agent A and the UV absorber can be added to the raw material solution before the pre-reaction, or the epoxy resin and diluent can be pre-reacted before the decolorizing agent A and the UV absorber are added to obtain component B.

[0023] In this invention, the color-reducing agent A can be a component known in the industry, for example, it can be the functional color-reducing agent DC510 developed by Hunan Petrochemical.

[0024] In this invention, the ultraviolet absorber can be any component with ultraviolet absorption in the industry, such as at least one of UV-1, UV-400, UV-9, and UV-329.

[0025] Preferably, the color-degrading agent A is 0.02 to 0.05 parts by weight;

[0026] Preferably, the amount of ultraviolet absorber is 0.03 to 0.1 parts by weight.

[0027] In this invention, the pre-reaction temperature is 70-80℃. Based on the innovative composition of the polyetheramine curing agent and diluent A, as well as the pre-reaction modification, the combined control of the pre-reaction temperature helps to further synergistically improve the modification effect of both, making them suitable for the preparation requirements of epoxy crystal soft glue, thereby improving the performance of epoxy crystal soft glue.

[0028] Preferably, the pre-reaction time is 1 to 5 hours, and more preferably 2 to 4 hours.

[0029] In this invention, the epoxy resin in component A is at least one of epoxy resin E44, epoxy resin CYD-128, and epoxy resin CYD-127, preferably a mixture of epoxy resin CYD-128 and epoxy resin CYD-127. This invention has found that using the aforementioned combined epoxy resin can further synergistically enhance the performance of the prepared crystal soft resin by combining it with the process described in this invention.

[0030] In this invention, component A further includes diluent B, color-reducing agent B, and defoamer;

[0031] In this invention, the diluent B comprises glycidyl ether compounds, preferably at least one of C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, and 1,4-butanediol diglycidyl ether.

[0032] In this invention, diluent B may also contain benzyl alcohol;

[0033] In this invention, the content of glycidyl ether compounds in diluent B is above 50 wt%.

[0034] In this invention, the color-reducing agent B includes DC510, a functional color-reducing agent developed by Hunan Petrochemical.

[0035] In this invention, the defoamer includes at least one of SF833, SF800, BYK141, and BYK530.

[0036] In this invention, component A comprises 80-90 parts by weight of epoxy resin, 10-20 parts by weight of diluent, 0.05-0.1 parts by weight of color-degrading agent B, and 0.2-1 parts by weight of defoamer.

[0037] In this invention, the weight ratio of component A to component B is 1.5 to 2.5:1, and more preferably 1.8 to 2.2:1.

[0038] In this invention, the curing reaction is carried out at room temperature. The curing time can be adjusted as needed, and considering production efficiency, it can be 12–30 hours.

[0039] The present invention also provides an epoxy crystal soft gel prepared by the preparation method described above.

[0040] The present invention also provides an application of the epoxy crystal soft glue described above, for coating on the surface of an object to form a crystal soft glue protective layer on the surface of the object;

[0041] In this invention, the surface of the object can be, for example, the surface of a craft ornament or a nameplate.

[0042] The present invention also provides an object with a protective layer of crystal soft glue on its surface, wherein the crystal soft glue on the surface is the epoxy crystal soft glue described in the present invention.

[0043] Beneficial effects

[0044] This invention innovatively pre-reacts the polyetheramine curing agent and diluent A, which helps to modify and reorganize the chain structure of the curing agent, and further composites and cures it with component B. This achieves synergy and can obtain crystal soft glue with better performance without omitting toughening components.

[0045] In this invention, the use of a preferred combination of curing agent and epoxy resin helps to further synergize with the pre-reaction post-curing process described in this invention, and helps to further synergistically improve the performance of the prepared crystal soft glue. Detailed Implementation

[0046] It can effectively solve the problems of poor adhesion, high cost and poor resistance to yellowing of existing crystal glue.

[0047] This invention discloses a typical epoxy crystal soft adhesive raw material formulation, which is composed of epoxy resin component A and curing agent component B mixed in a weight ratio of 1.5 to 2.5:1. The following examples are typical examples, and can be specified to 2:1.

[0048] The epoxy resin component A comprises, by weight fraction: 80-90 parts epoxy resin, 10-20 parts diluent, 0.05-0.1 parts color-reducing agent, and 0.2-1 parts defoamer;

[0049] The curing agent component B consists of 75-95 parts by weight of polyetheramine curing agent, 10-30 parts by weight of diluent, 0.02-0.05 parts by weight of color-degrading agent, and 0.03-0.1 parts by weight of UV absorber pre-reaction system.

[0050] The epoxy resin includes a mixture of epoxy resin E44, epoxy resin CYD-128, and epoxy resin CYD-127.

[0051] The diluent comprises at least one of C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, and 1,4-butanediol diglycidyl ether, and may also contain benzyl alcohol.

[0052] The defoamer includes one or a mixture of two of SF833, SF800, BYK141, and BYK530.

[0053] The light-shielding agent (ultraviolet absorber) includes one or more of UV-1, UV-400, UV-9, and UV-329.

[0054] The polyetheramine curing agent includes one or a mixture of polyetheramine D230, polyetheramine D400, and polyetheramine D2000.

[0055] The color-reducing agent mentioned is DC510, a functional color-reducing agent developed by Hunan Petrochemical.

[0056] In this invention, the combination B can be pre-reacted and then cured with component A to obtain the crystal soft glue.

[0057] The epoxy crystal adhesive of this invention has good adhesion to various material surfaces, high toughness, good color and transparency when used to make signs, ornaments and advertising nameplates, and excellent resistance to yellowing and relatively soft hardness after curing.

[0058] Example 1:

[0059] This invention discloses an epoxy crystal soft adhesive formulation and its preparation method, which consists of epoxy resin component A and curing agent B mixed in a weight ratio of 2:1.

[0060] Component A: The epoxy resin component A comprises, by weight fraction: 85 parts epoxy resin, 10 parts benzyl glycidyl ether, 5 parts benzyl alcohol, 0.4 parts defoamer SF833, and 0.06 parts color-degrading agent DC510. During preparation, the epoxy resin, diluent, defoamer, and color-degrading agent are added sequentially to a reaction vessel and stirred at 45±5℃ for 30–60 min to obtain component A. The epoxy resin is composed of 80 parts epoxy resin CYD-128 and 5 parts epoxy resin E44.

[0061] Component B: The curing agent component B, by weight fraction, comprises: 20 parts polyetheramine D230, 60 parts polyetheramine D2000, 20 parts C12-C14 alkyl glycidyl ether, 0.3 parts ultraviolet absorber UV-1, and 0.01 parts color-degrading agent DC510. In preparation, polyetheramine D230, polyetheramine D2000, and C12-C14 alkyl glycidyl ether are added sequentially to a reaction vessel, the temperature is controlled at 70-80℃ (marked as T), and the reaction is carried out for 2 hours. Finally, UV-1 and the color-degrading agent are added, and the mixture is stirred evenly to obtain component B (also known as curing agent B).

[0062] When using, add resin component A and curing agent component B in sequence and stir evenly. Then cure at room temperature for 24 hours.

[0063] Example 2:

[0064] This invention discloses an epoxy crystal soft adhesive formulation and its preparation method, which consists of epoxy resin component A and curing agent B mixed in a weight ratio of 2:1.

[0065] The epoxy resin component A comprises, by weight fraction: 88 parts epoxy resin, 12 parts C12-C14 alkyl glycidyl ether, 0.5 parts defoamer SF800, and 0.06 parts color-degrading agent DC510. During preparation, the epoxy resin, diluent, defoamer, and color-degrading agent are added sequentially to a reaction vessel and stirred at 45±5℃ for 30–60 min to obtain component A. The epoxy resin is composed of 80 parts of epoxy resin CYD-128 and 8 parts of epoxy resin CYD-127.

[0066] The curing agent component B comprises, by weight fraction: 10 parts polyetheramine D230, 70 parts polyetheramine D400, 13 parts benzyl alcohol, 7 parts benzyl glycidyl ether, 0.3 parts UV absorber UV-400 and 0.3 parts UV-9, and 0.01 parts color-degrading agent DC510. In preparation, polyetheramine D230, polyetheramine D400, benzyl alcohol, and benzyl glycidyl ether are added sequentially to a reaction vessel, the temperature is controlled at 70–80°C, and the reaction is carried out for 2 hours. Finally, UV-400, UV-9, and color-degrading agent DC510 are added, and the mixture is stirred for 30 minutes to obtain component B.

[0067] When using, add resin component A and curing agent component B in sequence and stir evenly. Then cure at room temperature for 24 hours.

[0068] Example 3:

[0069] This invention discloses an epoxy crystal soft adhesive formulation and its preparation method, which consists of epoxy resin component A and curing agent B mixed in a weight ratio of 2:1.

[0070] The epoxy resin component A comprises, by weight fraction: 90 parts epoxy resin CYD-128, 10 parts 1,4-butanediol diglycidyl ether, 0.5 parts defoamer BYK141, and 0.06 parts color-degrading agent DC510. During preparation, the epoxy resin, diluent, defoamer, and color-degrading agent are added sequentially to a reaction vessel and stirred at 45±5℃ for 30–60 min to obtain component A.

[0071] The curing agent component B comprises, by weight fraction: 5 parts polyetheramine D230, 60 parts polyetheramine D400, 20 parts polyetheramine D2000, 15 parts C12-C14 alkyl glycidyl ether, 0.5 parts UV absorber UV-329, and 0.01 parts color-degrading agent DC510. In preparation, polyetheramine D230, polyetheramine D400, polyetheramine D2000, and C12-C14 alkyl glycidyl ether are added sequentially to a reaction vessel, the temperature is controlled at 70-80℃, and the reaction is carried out for 2 hours. Finally, UV-329 and color-degrading agent DC510 are added, and the mixture is stirred for 30 minutes to obtain component B.

[0072] When using, add resin component A and curing agent component B in sequence and stir evenly. Then cure at room temperature for 24 hours.

[0073] Example 4:

[0074] This invention discloses an epoxy crystal soft adhesive and its preparation method, which is composed of epoxy resin component A and curing agent B mixed in a weight ratio of 2:1.

[0075] The epoxy resin component A comprises, by weight fraction: 90 parts epoxy resin CYD-128, 5 parts benzyl glycidyl ether, 5 parts benzyl alcohol, 0.5 parts defoamer BYK530, and 0.06 parts color-degrading agent DC510. During preparation, the epoxy resin, diluent, defoamer, and color-degrading agent are added sequentially to a reaction vessel and stirred at 45±5℃ for 30–60 min.

[0076] The curing agent component B comprises, by weight fraction: 8 parts polyetheramine D230, 65 parts polyetheramine D400, 17 parts polyetheramine D2000, 10 parts C12-C14 alkyl glycidyl ether, 0.8 parts ultraviolet absorber UV-1, and 0.01 parts color-degrading agent DC510. In preparation, polyetheramine D230, polyetheramine D400, polyetheramine D2000, and C12-C14 alkyl glycidyl ether are added sequentially to a reaction vessel, the temperature is controlled at 70-80℃, and the reaction is carried out for 2 hours. Finally, UV-1 and color-degrading agent DC510 are added, and the mixture is stirred for 30 minutes to obtain component B.

[0077] When using, add resin component A and curing agent component B in sequence and stir evenly. Then cure at room temperature for 24 hours.

[0078] The above embodiments were tested according to Q / SH 1085007-2020, measuring viscosity, platinum-cobalt color number, amine value, and Shore hardness (HA). The results are shown in Table 1.

[0079] Table 1 Test values ​​of Crystal Soft Rubber A / B materials

[0080]

[0081] The above embodiments were tested using a mechanical testing machine. The results showed that the tensile strength, tensile modulus, 90° peel strength, toughness, and adhesion of the embodiments were all good. The results are shown in Table 2.

[0082] Table 2. Mechanical Performance Test Results of Examples

[0083]

[0084] To address the key innovations of this application, several typical cases are presented to demonstrate that successful preparation can be achieved under all critical conditions, and that even better results can be obtained under preferred conditions, for example:

[0085] Example 5

[0086] Compared with Example 1, the only difference is that the epoxy resin is a single epoxy resin CYD-128, the total amount of epoxy resin and other operations and parameters are the same as in Example 1, and the resin component A and curing agent component B are added in sequence and stirred evenly. After curing, the hardness is about 50A, which meets the requirements of soft glue.

[0087] Example 6

[0088] Compared to Example 2, the only difference is that the curing agent used is a single D400, while the total amount of curing agent is the same as in Example 2. That is, D230 is missing, and the missing component is supplemented by an equal amount of D400. Other operations and parameters are the same as in Example 2. Resin component A and curing agent component B are added sequentially and stirred evenly. The hardness after curing is about 36A, but the curing time is twice as long as in Examples 1-5.

[0089] Comparative Example 1

[0090] Compared to Example 1, the only difference is that C12-C14 alkyl glycidyl ether was not added to component B, and the missing C12-C14 alkyl glycidyl ether was supplemented by benzyl alcohol, that is, the amount of benzyl alcohol used was 15 parts by weight. Other operations and parameters were the same as in Example 1. Resin component A and curing agent component B were added sequentially and stirred evenly. After curing, the hardness was about 70A, which was relatively high and did not achieve the effect of a soft glue.

[0091] Comparative Example 2

[0092] Compared to Example 1, the only difference is that in component B, no high-temperature reaction was performed; the components were physically mixed only at room temperature (25–35°C). All other operations and parameters were the same as in Example 1. Under the same curing time, components A and B did not cure completely, and the surface was not polymerized and dried, failing to meet the requirements for use as a soft adhesive. Furthermore, the inventors also conducted a case study with a pre-reaction temperature of 40–45°C, and the results were similar to those at room temperature.

[0093] The low-viscosity epoxy crystal soft adhesive provided by this invention has a reasonable formulation. After the resin and curing agent are mixed, the viscosity is low, the leveling and permeability are good, the toughness after curing is high, the adhesion is strong, the hardness is moderate, and the overall performance is good.

[0094] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art based on the above description should be included within the scope of protection of the present invention. The scope of protection of the present invention shall be defined by the appended claims.

Claims

1. A method for preparing epoxy crystal soft adhesive, characterized in that, A raw material solution containing a polyetheramine curing agent and diluent A is pre-reacted to obtain component B with curing ability. Component B is then mixed with component A containing epoxy resin and subjected to a curing reaction to obtain the epoxy crystal soft glue. The diluent A contains at least a glycidyl ether compound; The pre-reaction temperature is 60~90℃; The polyetheramine curing agent includes two or three of polyetheramine D230, polyetheramine D400, and polyetheramine D2000; The diluent A includes glycidyl ether compounds, wherein the glycidyl ether compound is at least one of C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, and 1,4-butanediol diglycidyl ether; In the raw material solution, the polyetheramine curing agent is 75-95 parts by weight and the diluent A is 10-30 parts by weight; In component A, the epoxy resin is two or more of epoxy resin E44, epoxy resin CYD-128, and epoxy resin CYD-127. The weight ratio of component A to component B is 1.5~2.5:

1.

2. The preparation method of epoxy crystal soft adhesive as described in claim 1, characterized in that, The polyetheramine curing agent includes a mixture of polyetheramine D230 and polyetheramine D400.

3. The preparation method of epoxy crystal soft adhesive as described in claim 1, characterized in that, The diluent A also contains benzyl alcohol.

4. The preparation method of epoxy crystal soft adhesive as described in claim 1, characterized in that, The solution system before or after the pre-reaction also contains color-degrading agent A and ultraviolet absorber; The color-reducing agent A includes DC510, a functional color-reducing agent developed by Hunan Petrochemical. The ultraviolet absorber includes at least one of UV-1, UV-400, UV-9, and UV-329; The color-degrading agent A has a weight ratio of 0.02~0.05 parts; The amount of ultraviolet absorber is 0.03 to 0.1 parts by weight.

5. The method for preparing epoxy crystal soft adhesive as described in claim 1, characterized in that, The pre-reaction temperature is 70~80℃; The pre-reaction time is 1-5 hours.

6. The method for preparing epoxy crystal soft adhesive as described in claim 1, characterized in that, Component A is a mixture of epoxy resin CYD-128 and epoxy resin CYD-127.

7. The method for preparing epoxy crystal soft adhesive as described in claim 1, characterized in that, Component A further includes diluent B, color-reducing agent B, and defoamer; The diluent B includes glycidyl ether compounds, which are at least one of C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, and 1,4-butanediol diglycidyl ether; The diluent B also contains benzyl alcohol; The color-reducing agent B includes DC510, a functional color-reducing agent developed by Hunan Petrochemical. The defoamer includes at least one of SF833, SF800, BYK141, and BYK530.

8. The method for preparing epoxy crystal soft adhesive as described in claim 7, characterized in that, In component A, the epoxy resin is 80-90 parts by weight, the diluent is 10-20 parts by weight, the color-degrading agent B is 0.05-0.1 parts by weight, and the defoamer is 0.2-1 parts by weight.

9. An epoxy crystal soft gel prepared by the preparation method according to any one of claims 1 to 8.

10. An application of the epoxy crystal soft adhesive according to any one of claims 1 to 8, characterized in that, It is used to coat the surface of an object to form a crystal soft gel protective layer on the surface of the object.

11. The application of the epoxy crystal soft adhesive as described in claim 10, characterized in that, The surface of the object is the surface of a craft ornament or nameplate.

12. An object with a surface coated with a crystal soft rubber protective layer, characterized in that, The surface-coated crystal soft glue is the epoxy crystal soft glue as described in any one of claims 1 to 8.

Images