Bisphenol A type epoxy resin crystal glue and preparation method thereof

Abstract

The invention discloses bisphenol A type epoxy resin crystal glue and a preparation method thereof. The polyester resin is obtained by reacting raw materials including a component A and a component B, the mass ratio of the component A to the component B is (1-3): 1; the component A comprises bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, a reactive diluent and a defoaming agent; the component B comprises alicyclic amine, polyether monoamine, bisphenol A epoxy resin and a reactive diluent; the polyester resin is prepared by the following steps: respectively preparing a component A and a component B, enabling bisphenol A epoxy resin and polyether monoamine to react through a fractional step method, adding a reactive diluent to obtain a precursor of the component B, slowly dripping the precursor into alicyclic amine to obtain the component B, and mixing the component A and the component B to obtain the polyester resin. Based on the synergistic effect of all the components, the transparency and yellowing resistance of the crystal glue are greatly improved on the premise of not needing an organic solvent, an accelerant and an antioxidant.

Description

Technical Field

[0001] The invention relates to yellowing-resistant crystal glue, in particular to bisphenol A type epoxy resin crystal glue and a preparation method thereof, belonging to the technical field of crystal glue. Background Art

[0002] The use of crystal glue can not only protect the surface of crafts and accessories, but also increase the gloss and brightness of the product surface. Crystal glue is also called crystal glue and fake crystal. Crystal glue on the market is generally divided into three categories: polyurethane crystal glue, acrylic, and epoxy resin glue. Bisphenol A epoxy resin crystal glue is a type of epoxy resin crystal glue. Bisphenol A epoxy resin glue has the best chemical corrosion resistance, but because of its relatively poor yellowing resistance and toughness, bisphenol A epoxy resin crystal glue has a small market share. In the prior art, antioxidants are often added to improve the aging resistance of bisphenol A epoxy resin, and accelerators are added to increase the curing speed. Most antioxidants are phenolic substances, which are easily oxidized and turned into dark substances, causing the crystal glue to change color; many accelerators are also mostly phenols or tertiary amines, which can easily make the crystal glue have poor anti-yellowing effect, or poor mechanical properties after curing, which directly affects the use. Summary of the invention

[0003] In view of the problems existing in the prior art, the first purpose of the present invention is to provide a bisphenol A epoxy resin crystal glue. Based on the synergistic effect between the various components, the crystal glue does not require organic solvents, promoters and antioxidants, and can greatly improve the weather resistance, color stability and glossiness of the crystal glue. It also has a suitable curing rate, thereby ensuring that the crystal glue has excellent transparency and yellowing resistance.

[0004] The second object of the present invention is to provide a method for preparing bisphenol A epoxy resin crystal glue, which stimulates the synergistic effect between components by strictly controlling the process parameters between each step, especially the step-by-step preparation process in component B, thereby ensuring the reaction activity of the material while improving the stability and weather resistance of the material, thereby greatly improving the comprehensive performance of the crystal glue.

[0005] In order to achieve the above technical purpose, the present invention provides a bisphenol A type epoxy resin crystal glue, which is composed of component A and component B; the mass ratio of component A to component B is 1 to 3:1;

[0006] The component A comprises the following components by mass percentage: 60-80% of bisphenol A epoxy resin, 5-15% of hydrogenated bisphenol A epoxy resin, 10-30% of active diluent and 0.2-0.5% of defoamer;

[0007] The B component comprises the following components in percentage by weight: 35-55% of alicyclic amine, 15-45% of polyether monoamine, 10-25% of bisphenol A epoxy resin and 10-20% of active diluent.

[0008] As a preferred solution, the active diluent is C 12-14 Alkyl glycidyl ether and / or glycidyl neodecanoate.

[0009] The active diluent used in the present invention is a long carbon chain monoepoxy active diluent. On the one hand, the long carbon chain can improve the brittleness of the epoxy resin and increase the flexibility of the epoxy resin. The addition of the monoepoxy group can reduce the viscosity and reaction activity of the bisphenol A type epoxy resin, and it is not easy to generate bubbles in the system. On the other hand, the active diluent is a macromolecular substance, which can improve the product's ultraviolet radiation resistance, chemical resistance and stability by generating a steric effect.

[0010] As a preferred solution, the alicyclic amine is at least one of isophorone diamine, 1-3-cyclohexyl dimethylamine and 4-4-diaminodicyclohexyl methane.

[0011] As a preferred solution, the polyether monoamine is one or more of Heinzman's M-1000, M-2070, M-2095 and M-3085. The polyether monoamine used in the present invention can greatly improve the antioxidant properties of the crystal glue, thereby improving the color stability of the product, and because the polyether monoamine is essentially a monoamine, its reaction activity is lower than that of diamine and polyamine compounds, and the reaction rate can be well controlled, which is convenient for the discharge of bubbles during the stirring process.

[0012] The polyether monoamine used in the present invention can well regulate the reaction rate of alicyclic amine and epoxy resin. Among the polyether amines, the reaction activity of monoamine is lower than that of diamine and polyamine compounds, which can facilitate the discharge of bubbles during the reaction. At the same time, the color stability of polyether monoamine is also better than that of polyether diamine and polyether polyamine, so that the product has excellent color stability.

[0013] As a preferred solution, the bisphenol A type epoxy resin is at least one of 127, 128 and 128E type liquid epoxy resins.

[0014] As a preferred solution, the bisphenol A type epoxy resin is 127 and / or 128 type liquid epoxy resin. Further preferably, the bisphenol A type epoxy resin is NPEL-127 and / or NPEL-128 type liquid epoxy resin.

[0015] The present invention also provides a method for preparing bisphenol A epoxy resin crystal glue, comprising the steps of uniformly mixing raw materials including bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, active diluent and defoaming agent in a reaction kettle to obtain component A; uniformly mixing bisphenol A epoxy resin and polyether monoamine in a reaction kettle to react, adding active diluent after the reaction to mix uniformly to obtain component B precursor; and slowly dripping the component B precursor into a reaction kettle filled with alicyclic amine to obtain component B.

[0016] As a preferred solution, the reactor is filled with a protective atmosphere, which is at least one of nitrogen, argon and helium.

[0017] As a preferred solution, the reaction conditions of the bisphenol A epoxy resin and the polyether monoamine are: temperature of 60 to 120° C. and time of 1 to 6 hours.

[0018] As a preferred solution, the conditions for the B component precursor dropwise addition process are: temperature ≤75°C, and dropwise addition time is 1 to 3 hours.

[0019] As a preferred solution, after the B component precursor is added dropwise, a heat preservation reaction is required, and the conditions are: temperature of 50-75° C. and time of 2-4 hours.

[0020] Compared with the prior art, the beneficial technical effects of the present invention are:

[0021] 1) The bisphenol A epoxy resin crystal glue provided by the present invention can greatly improve the weather resistance, color stability, glossiness and suitable curing rate of the crystal glue based on the synergistic effect between the various components without the need for organic solvents, promoters and antioxidants, thereby ensuring that the crystal glue has excellent transparency and yellowing resistance.

[0022] 2) The preparation method provided by the present invention stimulates the synergistic effect between the components by strictly controlling the process parameters between each step, especially the step-by-step preparation process in component B, which ensures the reaction activity of the material while improving the stability and weather resistance of the material, thereby greatly improving the comprehensive performance of the crystal glue.

[0023] 3) In the technical solution provided by the present invention, hydrogenated bisphenol A epoxy resin and active diluent are selected to optimize the weather resistance of liquid bisphenol A epoxy resin, improve its brittleness and reduce viscosity, and improve the fluidity of the resin. When component A containing hydrogenated bisphenol A epoxy resin reacts with component B, the system flexibility of the crystal glue is improved under the action of the active diluent with the polyether monoamine in component B, and the curing reaction rate of the crystal glue is adjusted, thereby obtaining a crystal glue product with high transparency, high yellowing resistance and moderate elasticity. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a color change diagram of Examples 1 to 3 of the present invention and commercially available crystal glue after being oxidized at room temperature for one year. DETAILED DESCRIPTION

[0025] The present invention is further described in detail below in conjunction with the embodiments, but is not limited thereto. Of course, this cannot be used to limit the scope of the present invention, and therefore equivalent changes made according to the claims of the present invention still fall within the scope covered by the present invention.

[0026] Example 1

[0027] The weight ratio of component A to component B is component A: component B = 2:1;

[0028] The A component is made of raw materials containing the following weight percentages: 60% bisphenol A epoxy resin, 15% hydrogenated bisphenol A epoxy resin, 24.8% active diluent, and 0.2% defoamer;

[0029] In component A: the bisphenol A epoxy resin is NPEL-127 produced by Nanya Electronic Materials (Kunshan) Co., Ltd.; the active diluent is C12-14 alkyl glycidyl ether;

[0030] The B component is made of raw materials containing the following weight percentages: 49% alicyclic amine, 20.5% polyether monoamine, 20% bisphenol A type epoxy resin, and 10.5% active diluent, wherein the alicyclic amine is isophorone diamine.

[0031] In component B: the polyether monoamine is M-1000 produced by Heinz Mann, the bisphenol A epoxy resin is NPEL-127 produced by Nanya Electronic Materials (Kunshan) Co., Ltd., the active diluent is C12-14 alkyl glycidyl ether, and the defoamer is polyether siloxane.

[0032] The preparation process of crystal glue is:

[0033] 1) adding bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, C12-14 alkyl glycidyl ether and defoamer into a reaction kettle in sequence and stirring evenly to obtain Group A of bisphenol A epoxy resin crystal glue of Example 1;

[0034] 2) Add bisphenol A epoxy resin NPEL-127 and polyether monoamine M-1000 into a reactor filled with nitrogen, stir evenly and heat to 75°C, react at this temperature for 5 hours, then add active diluent C 12-14 Alkyl glycidyl ether, stir evenly to obtain component B precursor;

[0035] 3) The precursor of component B is dripped into the reaction kettle containing isophorone diamine at a temperature of

[0036] The alicyclic amine isophorone diamine was added into a reaction kettle filled with nitrogen, and the product of step 2 was added dropwise at a temperature of 50°C. After the addition was completed, the reaction temperature was maintained at 60°C and the reaction was carried out for 3 hours to obtain component B of the bisphenol A epoxy resin crystal glue of this embodiment 1.

[0037] 4) Mix component A and component B evenly, let stand and solidify to obtain crystal glue.

[0038] Example 2

[0039] The preparation process of this embodiment is exactly the same as that of embodiment 1, except that:

[0040] The weight ratio of component A to component B is component A: component B = 2.5:1.

[0041] The A component is made of raw materials containing the following weight percentages: 70% bisphenol A epoxy resin, 10% hydrogenated bisphenol A epoxy resin, 19.7% active diluent, and 0.3% defoaming agent.

[0042] In component A: the active diluent is C 12-14 Mixture of alkyl glycidyl ether and neodecanoic acid glycidyl ester, C 12-14 The volume ratio of alkyl glycidyl ether to neodecanoic acid glycidyl ester is 1:1.

[0043] The B component is made of raw materials containing the following weight percentages: 45% alicyclic amine, 30% polyether monoamine, 15% bisphenol A type epoxy resin, and 10% active diluent.

[0044] In component B: the alicyclic amine is a mixture of isophorone diamine and 1-3-cyclohexyl dimethylamine, and the molar ratio of isophorone diamine to 1-3-cyclohexyl dimethylamine is 2:1; the polyether monoamine is Henstmann's M-2070, and the active diluent is glycidyl neodecanoate.

[0045] Example 3

[0046] The preparation process of this embodiment is exactly the same as that of embodiment 1, except that:

[0047] The weight ratio of component A to component B is component A: component B = 3:1.

[0048] The A component is made of raw materials containing the following weight percentages: 78% of bisphenol A epoxy resin; 8% of hydrogenated bisphenol A epoxy resin; 13.5% of active diluent; and 0.5% of defoaming agent.

[0049] In component A: the active diluent is a mixture of glycidyl neodecanoate.

[0050] The B component is made of raw materials containing the following weight percentages: 39% alicyclic amine, 35% polyether monoamine, 10% bisphenol A type epoxy resin, and 16% active diluent.

[0051] In component B: the alicyclic amine is a mixture of isophorone diamine and 4-4-diaminodicyclohexylmethane, and the molar ratio of isophorone diamine to 4-4-diaminodicyclohexylmethane is 1:1; the polyether monoamine is a mixture of Henstmann's M-1000 and M-3085, and the molar ratio of M-1000 to M-3085 is 1:2; and the active diluent is glycidyl neodecanoate.

[0052] The present invention conducts yellowing resistance test on Examples 1 to 3. The test process refers to the "Determination of discoloration (yellowing) performance of adhesives" (GB / T 39294-2020). The test process is as follows: the sample in each embodiment is divided into five parts, and the light source rated power is 300W, the ultraviolet light wavelength is 250nm~400nm, and the ultraviolet light intensity is 25±0.4W / m 2 The irradiation was continued for 3000 hours, and the bulb was replaced every 1000 hours. After the irradiation, the crystal glue was taken out and compared with the gray standard card in a standard light source box equipped with a D65 light source. The use of the gray standard card was in accordance with the "Gray Sample Card for Assessing Color Change" (GB / T 250-2008). The worst value of the 5 test results was taken as the test result. The test results are shown in Table 1.

[0053] Table 1 Yellowing resistance test results of crystal glue obtained in Examples 1 to 3

[0054] Fastness grade CIELAB color difference Example 1 5 0.2 Example 2 5 0.1 Example 3 5 0.1

[0055] It can be seen from Table 1 that the crystal glue provided by the present invention has excellent yellowing resistance. Under continuous irradiation for 3000 hours, there is almost no change and it still has high transmittance. Furthermore, the crystal glue obtained in Examples 1 to 3 and the commercially available Santai 883 epoxy resin crystal glue were subjected to long-term oxidation at room temperature. The anti-yellowing deformation performance is significantly better. Figure 1 As shown, most common bisphenol A epoxy resin crystal glues on the market turn yellow within 1 year, while the bisphenol A epoxy resin crystal glue provided by the present invention has outdoor yellowing resistance for more than 3 years.

Claims

1. A bisphenol A epoxy resin crystal glue, characterized in that: It is composed of component A and component B; the mass ratio of component A to component B is 1 to 3:1; The component A comprises the following components by mass percentage: 60-80% of bisphenol A epoxy resin, 5-15% of hydrogenated bisphenol A epoxy resin, 10-30% of active diluent and 0.2-0.5% of defoamer; The B component comprises the following components in percentage by weight: 35-55% of alicyclic amine, 15-45% of polyether monoamine, 10-25% of bisphenol A epoxy resin and 10-20% of active diluent.

2. The bisphenol A epoxy resin crystal glue according to claim 1, characterized in that: The active diluent is C 12-14 Alkyl glycidyl ether and / or glycidyl neodecanoate.

3. The bisphenol A epoxy resin crystal glue according to claim 1, characterized in that: The alicyclic amine is at least one of isophorone diamine, 1-3 cyclohexane dimethylamine and 4-4 diaminodicyclohexylmethane.

4. The bisphenol A epoxy resin crystal glue according to claim 1, characterized in that: The polyether monoamine is one or more of Heinzmann's M-1000, M-2070, M-2095 and M-3085.

5. The bisphenol A epoxy resin crystal glue according to claim 1, characterized in that: The bisphenol A type epoxy resin is at least one of 127, 128 and 128E type liquid epoxy resins.

6. The method for preparing a bisphenol A type epoxy resin crystal glue according to any one of claims 1 to 5, characterized in that: The raw materials including bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, active diluent and defoaming agent are mixed evenly in a reaction kettle to obtain component A; the bisphenol A epoxy resin and polyether monoamine are mixed evenly in a reaction kettle to react, and after the reaction is completed, the active diluent is added and mixed evenly to obtain a precursor of component B; the precursor of component B is slowly dripped into the reaction kettle filled with alicyclic amine to obtain component B.

7. The bisphenol A epoxy resin crystal glue according to claim 6, characterized in that: The reactor is filled with a protective atmosphere, which is at least one of nitrogen, argon and helium.

8. The method for preparing bisphenol A type epoxy resin crystal glue according to claim 6, characterized in that: The reaction conditions of the bisphenol A epoxy resin and the polyether monoamine are: temperature of 60-120° C. and time of 1-6 hours.

9. The method for preparing bisphenol A epoxy resin crystal glue according to claim 6, characterized in that: The conditions for the B component precursor dropwise addition process are: temperature ≤75°C, and dropwise addition time 1 to 3 hours.

10. The method for preparing a bisphenol A type epoxy resin crystal glue according to claim 6, characterized in that After the B component precursor is added, it is necessary to carry out a heat preservation reaction at a temperature of 50 to 75°C. The time is 2 to 4 hours.

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