Epoxy crystal flexible glue as well as preparation and application thereof

Abstract

The invention belongs to the field of crystal glue, and particularly discloses a preparation method of epoxy crystal flexible glue, which comprises the following steps: pre-reacting a raw material solution containing a polyether amine curing agent and a diluent A to obtain a component B with curing capacity, mixing the obtained component B with a component A containing epoxy resin, and carrying out curing reaction to obtain the epoxy crystal flexible glue, the diluent A at least comprises a glycidyl ether compound; the pre-reaction temperature is 60-90 DEG C; the invention further discloses the crystal flexible glue prepared by the preparation method and application of the crystal flexible glue. According to the process disclosed by the invention, the epoxy crystal flexible glue with excellent performance can be obtained without an auxiliary agent.

Description

Technical Field

[0001] The present invention relates to the technical field of epoxy crystal glue, and in particular to the technical field of epoxy crystal soft glue. Background Art

[0002] Crystal glue mainly includes crystal hard glue and crystal soft glue. For example, the Chinese patent document with publication number CN110408356A discloses a formula of epoxy polyurethane crystal glue. The Chinese patent document with publication number CN109988481A discloses a low-viscosity quick-setting crystal glue. The Chinese patent document with publication number CN106366719A discloses a mildew-proof light-curing crystal glue. The existing technology mainly includes crystal hard glue, and crystal soft glue is relatively rare.

[0003] Epoxy crystal soft glue is composed of high-purity epoxy resin and curing agent. It has the advantages of environmental protection, low odor, non-toxicity, and easy operation. The cured product is crystal clear, water-resistant, and corrosion-resistant. Using crystal soft glue can protect the surface of craft accessories, nameplates, etc., and can also increase the gloss of the product surface.

[0004] However, existing crystal soft glue mostly uses diethylenetriamine and p-hydroxybenzenesulfonic acid as curing agents, and most of them need to add toughening agents such as polysulfide rubber, nitrile rubber, gelatin, etc. to increase the toughness of the system. The addition of toughening agents increases the cost of crystal glue, 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 solve the deficiencies in the prior art, the purpose of the present invention is to provide a method for preparing epoxy crystal soft glue, aiming to provide a non-toughened, low-cost crystal soft glue that also has excellent adhesion and softness.

[0006] The second purpose of the present invention is to provide epoxy crystal soft glue obtained by the preparation method.

[0007] The third purpose of the present invention is to provide the application of the epoxy crystal soft glue in the surface protection of craft accessories and nameplates.

[0008] The fourth object of the present invention is to provide an object compounded with the crystal soft glue protective layer of the present invention.

[0009] In view of the problem that the crystal glue is difficult to meet the quality requirements of the crystal soft glue due to the lack of toughening components, the present invention provides the following improvement scheme:

[0010] A method for preparing epoxy crystal soft glue, comprising pre-reacting a raw material solution containing a polyetheramine curing agent and a diluent A to obtain a component B with curing ability, mixing the obtained component B with a component A containing an epoxy resin, and performing a curing reaction to obtain the epoxy crystal soft glue;

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

[0012] The temperature of the preliminary reaction is 60 to 90°C.

[0013] The present invention innovatively pre-reacts the polyetheramine curing agent and diluent A, and further cooperates with the glycidyl ether compound component and the joint control of the pre-reaction temperature, which helps to modify and reorganize the chain segment structure of the curing agent, grow the molecular chain, increase the toughness of the curing agent, and further composite-cured it with component A, thereby achieving synergy, and can obtain a crystal soft glue with better performance without omitting the toughening component.

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

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

[0016] The present invention unexpectedly discovered that the innovative use of the preferred combined curing agent helps to further cooperate with the pre-reaction process described in the present invention, and helps to further synergistically improve the performance of the prepared crystal soft glue.

[0017] In the present invention, a polyetheramine curing agent and a glycidyl ether compound are innovatively used for pre-reaction. By utilizing the combination of the structures of the two and the pre-reaction method, the segment structure of the curing agent can be modified and reorganized, thereby avoiding conventional toughening additives and obtaining an epoxy crystal soft glue that meets the use requirements of the crystal soft glue.

[0018] In the present invention, in the diluent A, the glycidyl ether compound is at least one of C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, and 1,4-butanediol diglycidyl ether;

[0019] Preferably, the diluent A is also allowed to contain benzyl alcohol.

[0020] Preferably, the content of the glycidyl ether compound in the diluent A is above 20 wt.%, more preferably 30 to 50 wt.%. Under the preferred ratio, the performance of the prepared crystal soft glue can be further synergistically improved.

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

[0022] In the present invention, the solution system before or after the pre-reaction further contains a color-reducing agent A and a UV absorber. For example, the color-reducing agent A and the UV absorber may be added to the raw material solution in advance and then subjected to a pre-reaction, or the color-reducing agent A and the UV absorber may be added after the epoxy resin and the diluent are pre-reacted to obtain the component B.

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

[0024] In the present invention, the ultraviolet absorber can be any component with ultraviolet absorption in the industry, for example, it can include at least one of UV-1, UV-400, UV-9, and UV-329;

[0025] Preferably, the weight portion of the color reducing agent A is 0.02 to 0.05 parts;

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

[0027] In the present invention, the pre-reaction temperature is 70-80°C; in the present invention, based on the components of the polyetheramine curing agent, diluent A and the pre-reaction modification innovation, the pre-reaction temperature is further coordinated with the joint control, which helps to further synergistically improve the modification effects of the two, so that it adapts to the preparation requirements of the epoxy crystal soft glue, thereby improving the performance of the epoxy crystal soft glue.

[0028] Preferably, the pre-reaction time is 1 to 5 hours, and further can be 2 to 4 hours.

[0029] In the present invention, in the component A, the epoxy resin 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. The present invention has found that the use of the combined epoxy resin can further cooperate with the process of the present invention, which helps to further improve the performance of the prepared crystal soft glue.

[0030] In the present invention, the component A further comprises a diluent B, a color reducing agent B and a defoaming agent;

[0031] In the present invention, the diluent B comprises a glycidyl ether compound, preferably at least one of C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, and 1,4-butanediol diglycidyl ether;

[0032] In the present invention, the diluent B is also allowed to contain benzyl alcohol;

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

[0034] In the present invention, the color reducing agent B includes the functional color reducing agent DC510 developed by Hunan Petrochemical;

[0035] In the present invention, the defoaming agent includes at least one of SF833, SF800, BYK141 and BYK530.

[0036] In the present invention, in the component A, the weight portion of epoxy resin is 80-90 parts, the weight portion of diluent is 10-20 parts, the weight portion of decolorizing agent B is 0.05-0.1 parts, and the weight portion of defoaming agent is 0.2-1 parts.

[0037] In the present invention, the weight ratio of component A to component B is 1.5 to 2.5:1, and may further be 1.8 to 2.2:1.

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

[0039] The invention also provides an epoxy crystal soft glue prepared by the preparation method.

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

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

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

[0043] Beneficial Effects

[0044] The present invention innovatively pre-reacts the polyetheramine curing agent and diluent A, which helps to modify and reorganize the segment structure of the curing agent, and further composite-cures it with component B, thereby achieving synergy and obtaining a crystal soft glue with better performance without toughening components.

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

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

[0047] A typical raw material formula of epoxy crystal soft glue of the present invention 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 cases are listed as typical examples, and all of them can be specifically 2:1.

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

[0049] The curing agent B component is 75-95 parts by weight of a polyetheramine curing agent, 10-30 parts by weight of a diluent, 0.02-0.05 parts by weight of a color reducing agent, and 0.03-0.1 parts by weight of a 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 includes at least one of C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, and 1,4-butanediol diglycidyl ether, and is also allowed to contain benzyl alcohol.

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

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

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

[0055] The color reducing agent is the functional color reducing agent DC510 developed by Hunan Petrochemical.

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

[0057] The epoxy crystal glue of the present invention has good adhesion to the surfaces of various materials and high toughness. It has good color and permeability when making sign ornaments and advertising nameplates. It has excellent yellowing resistance and relatively soft hardness after curing.

[0058] Embodiment 1:

[0059] The invention discloses an epoxy crystal soft glue formula and a preparation method thereof. The epoxy resin A component and a curing agent B are mixed in a weight ratio of 2:1.

[0060] Component A: The epoxy resin component A includes, by weight, 85 parts of epoxy resin, 10 parts of benzyl glycidyl ether, 5 parts of benzyl alcohol, 0.4 parts of defoamer SF833, and 0.06 parts of color reducer DC510. During preparation, epoxy resin, diluent, defoamer, and color reducer are sequentially added to a reaction kettle, stirred at 45±5°C for 30 to 60 minutes, and material A is obtained. The epoxy resin is mixed with 80 parts of epoxy resin CYD-128 and 5 parts of epoxy resin E44.

[0061] Component B: The curing agent component B includes, by weight, 20 parts of polyetheramine D230, 60 parts of polyetheramine D2000, 20 parts of C12-C14 alkyl glycidyl ether, 0.3 parts of ultraviolet absorber UV-1, and 0.01 parts of decolorizing agent DC510. During preparation, polyetheramine D230, polyetheramine D2000, and C12-C14 alkyl glycidyl ether are sequentially added to a reaction kettle, the temperature is controlled at 70-80°C (marked as T), the reaction is carried out for 2 hours, and finally UV-1 and decolorizing agent are added, and the mixture is stirred evenly to obtain material B (also called 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] Embodiment 2:

[0064] The invention discloses an epoxy crystal soft glue formula and a preparation method thereof. The epoxy resin A component and a curing agent B are mixed in a weight ratio of 2:1.

[0065] The epoxy resin component A includes, by weight, 88 parts of epoxy resin, 12 parts of C12-C14 alkyl glycidyl ether, 0.5 parts of defoamer SF800, and 0.06 parts of color reducer DC510. During preparation, the epoxy resin, diluent, defoamer, and color reducer are sequentially added to a reaction kettle, stirred at 45±5°C for 30 to 60 minutes, and material A is obtained. The epoxy resin is mixed with 80 parts of epoxy resin CYD-128 and 8 parts of epoxy resin CYD-127.

[0066] The curing agent B component includes, by weight, 10 parts of polyetheramine D230, 70 parts of polyetheramine D400, 13 parts of benzyl alcohol, 7 parts of benzyl glycidyl ether, 0.3 parts of ultraviolet absorber UV-400 and 0.3 parts of UV-9, and 0.01 parts of decolorizing agent DC510. During preparation, polyetheramine D230, polyetheramine D400, benzyl alcohol, and benzyl glycidyl ether are sequentially added into a reaction kettle, the temperature is controlled at 70-80°C, the reaction is carried out for 2 hours, and finally UV-400, UV-9, and decolorizing agent DC510 are added, and the mixture is stirred for 30 minutes to obtain material 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] Embodiment 3:

[0069] The invention discloses an epoxy crystal soft glue formula and a preparation method thereof. The epoxy resin A component and a curing agent B are mixed in a weight ratio of 2:1.

[0070] The epoxy resin component A includes, by weight, 90 parts of epoxy resin CYD-128, 10 parts of 1,4-butanediol diglycidyl ether, 0.5 parts of defoamer BYK141, and 0.06 parts of color reducer DC510. During preparation, the epoxy resin, diluent, defoamer, and color reducer are sequentially added to a reaction kettle, stirred at 45±5°C for 30 to 60 minutes, and material A is obtained.

[0071] The curing agent B component includes, by weight, 5 parts of polyetheramine D230, 60 parts of polyetheramine D400, 20 parts of polyetheramine D2000, 15 parts of C12-C14 alkyl glycidyl ether, 0.5 parts of ultraviolet absorber UV-329, and 0.01 parts of decolorizing agent DC510. During preparation, polyetheramine D230, polyetheramine D400, polyetheramine D2000, and C12-C14 alkyl glycidyl ether are sequentially added into a reaction kettle, the temperature is controlled at 70-80°C, the reaction is carried out for 2 hours, and finally UV-329 and decolorizing agent DC510 are added, and the mixture is stirred for 30 minutes to obtain material 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] Embodiment 4:

[0074] The invention discloses an epoxy crystal soft glue and a preparation method thereof. The epoxy resin A component and a curing agent B are mixed in a weight ratio of 2:1.

[0075] The epoxy resin component A includes, by weight, 90 parts of epoxy resin CYD-128, 5 parts of benzyl glycidyl ether, 5 parts of benzyl alcohol, 0.5 parts of defoamer BYK530, and 0.06 parts of color reducing agent DC510. During preparation, the epoxy resin, diluent, defoamer, and color reducing agent are sequentially added to a reaction kettle and stirred at 45±5°C for 30 to 60 minutes.

[0076] The curing agent B component includes, by weight, 8 parts of polyetheramine D230, 65 parts of polyetheramine D400, 17 parts of polyetheramine D2000, 10 parts of C12-C14 alkyl glycidyl ether, 0.8 parts of ultraviolet absorber UV-1, and 0.01 parts of decolorizing agent DC510. During preparation, polyetheramine D230, polyetheramine D400, polyetheramine D2000, and C12-C14 alkyl glycidyl ether are sequentially added into a reaction kettle, the temperature is controlled at 70-80° C., the reaction is carried out for 2 hours, and finally UV-1 and decolorizing agent DC510 are added, and the mixture is stirred for 30 minutes to obtain material 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 examples were tested according to Q / SH 1085007-2020 to test viscosity, platinum cobalt color number, amine value, and Shore hardness HA. The results are shown in Table 1:

[0079] Table 1 Crystal soft glue A / B material test values

[0080]

[0081] The above embodiment was tested, and the tensile strength, tensile modulus, 90° peel strength, toughness and adhesive force of the above embodiment were measured by a mechanical testing machine, and the results are shown in Table 2:

[0082] Table 2 Mechanical properties test results of the embodiment

[0083]

[0084] In view of the key innovation of this application, a number of typical cases are set up to prove that under key conditions, they can be successfully prepared, and under optimal conditions, better effects can be obtained, 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 epoxy resin dosage and other operations and parameters are the same as Example 1, the resin component A and the curing agent component B are added in sequence and stirred evenly, and the hardness after curing is about 50A, which meets the requirements of soft glue.

[0087] Example 6

[0088] Compared with Example 2, the only difference is that the curing agent used in the curing agent is a single D400, and the total amount of the curing agent is the same as that 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. The resin component A and the curing agent component B are added in sequence and stirred evenly. The hardness after curing is about 36A, but compared with Examples 1 to 5, the curing time is doubled.

[0089] Comparative Example 1

[0090] Compared with Example 1, the only difference is that no C12-C14 alkyl glycidyl ether is added to component B, and the missing C12-C14 alkyl glycidyl ether is supplemented by benzyl alcohol, that is, the amount of benzyl alcohol is 15 parts by weight. Other operations and parameters are the same as in Example 1. The resin component A and the curing agent component B are added in sequence and stirred evenly. After curing, the hardness is about 70A, the hardness is relatively high, and the soft glue effect cannot be achieved.

[0091] Comparative Example 2

[0092] Compared with Example 1, the only difference is that in component B, no high temperature reaction is performed, and the components are only physically mixed at room temperature (25-35°C), and the other operations and parameters are the same as in Example 1. Under the same curing time of component A and component B, the curing is incomplete, the surface is not polymerized and the surface is dry, and the composite soft glue cannot be used. In addition, the inventors also made a case of pre-reaction at 40-45°C, and the phenomenon is similar to the room temperature result.

[0093] The low-viscosity epoxy crystal soft glue provided by the invention has a reasonable formula, low viscosity after the resin and the curing agent are mixed, good leveling and permeability, high toughness after curing, strong bonding force, moderate hardness and good comprehensive performance.

[0094] The above description is only a preferred specific implementation of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art based on the above description should be included in the protection scope of the present invention. The scope of the present invention shall be defined by the attached claims as the protection scope.

Claims

1. A method for preparing epoxy crystal soft glue, characterized in that: Pre-reacting a raw material solution containing a polyetheramine curing agent and a diluent A to obtain a component B with curing ability, mixing the obtained component B with a component A containing an epoxy resin, and performing a curing reaction to obtain the epoxy crystal soft glue; The diluent A at least comprises a glycidyl ether compound; The temperature of the preliminary reaction is 60 to 90°C.

2. The method for preparing the epoxy crystal soft glue according to claim 1, characterized in that: The polyetheramine curing agent includes a mixture of one or more of polyetheramine D230, polyetheramine D400, and polyetheramine D2000; Preferably, the polyetheramine curing agent includes a mixture of polyetheramine D230 and polyetheramine D400.

3. The method for preparing the epoxy crystal soft glue according to claim 1, characterized in that: The diluent A comprises a glycidyl ether compound, preferably at least one of C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, and 1,4-butanediol diglycidyl ether; Preferably, the diluent A is also allowed to contain benzyl alcohol.

4. The method for preparing epoxy crystal soft glue according to claim 1, characterized in that: In the raw material solution, the weight portion of the polyetheramine curing agent is 75 to 95 parts, and the weight portion of the diluent A is 10 to 30 parts.

5. The method for preparing the epoxy crystal soft adhesive according to any one of claims 1 to 4, characterized in that: A color reducing agent A and an ultraviolet absorber are also added to the solution system before or after the pre-reaction; Preferably, the color reducing agent A includes the functional color reducing agent DC510 developed by Hunan Petrochemical; Preferably, the ultraviolet absorber includes at least one of UV-1, UV-400, UV-9, and UV-329; Preferably, the weight portion of the color reducing agent A is 0.02 to 0.05 parts; Preferably, the weight portion of the ultraviolet absorber is 0.03 to 0.1 parts.

6. The method for preparing the epoxy crystal soft adhesive according to any one of claims 1 to 5, characterized in that: 70-80°C for pre-reaction; Preferably, the pre-reaction time is 1 to 5 hours.

7. The method for preparing epoxy crystal soft glue according to claim 1, characterized in that: In the component A, the epoxy resin 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.

8. The method for preparing the epoxy crystal soft adhesive according to claim 1 or 7, characterized in that: The component A further comprises a diluent B, a color reducing agent B and a defoaming agent; Preferably, the diluent B comprises a glycidyl ether compound, preferably at least one of C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, and 1,4-butanediol diglycidyl ether; Preferably, the diluent B is also allowed to contain benzyl alcohol; Preferably, the color reducing agent B includes the functional color reducing agent DC510 developed by Hunan Petrochemical; Preferably, the defoaming agent includes at least one of SF833, SF800, BYK141, and BYK530.

9. The method for preparing epoxy crystal soft glue according to claim 8, characterized in that: In the component A, the weight portion of epoxy resin is 80-90 parts, the weight portion of diluent is 10-20 parts, the weight portion of color reducing agent B is 0.05-0.1 parts, and the weight portion of defoaming agent is 0.2-1 parts.

10. The method for preparing epoxy crystal soft adhesive according to any one of claims 1 to 9, characterized in that: The weight ratio of component A to component B is 1.5-2.5:

1.

11. An epoxy crystal soft glue obtained by the preparation method according to any one of claims 1 to 10.

12. An application of the epoxy crystal soft adhesive according to any one of claims 1 to 11, characterized in that: Used to coat the surface of an object to form a crystal soft glue protective layer on the surface of the object; Preferably, the surface of the object is the surface of a craft ornament or a nameplate.

13. An object having a crystal soft adhesive protective layer on its surface, characterized in that: The surface-compounded crystal soft glue is the epoxy crystal soft glue described in any one of claims 1 to 11.

Images