Clean plate glue and preparation method thereof

Abstract

The invention relates to the technical field of adhesives, in particular to clean plate glue and a preparation method thereof.The clean plate glue comprises a main agent and a curing agent, and the main agent at least comprises, by weight, 40-60 parts of hydroxyl compounds, 4-9 parts of ester plasticizers, 30-50 parts of filler and 2-4 parts of auxiliaries; the hydroxyl compound at least comprises castor oil, polyether polyol and micromolecular polyol; the hydroxyl value of the polyether polyol is 300 to 400 mgKOH / g; the micromolecular polyol is propylene glycol; the mass ratio of the micromolecular polyol to the ester plasticizer is (0.5-1.5): (4-6); the ester plasticizer is fatty acid methyl ester, has a relatively long active period and open time under a high-temperature condition (more than 35 DEG C) in summer, meets the bonding requirements and processing requirements of a surface material and a core material in the clean board, and has a very high market application value.

Description

Technical Field

[0001] The invention relates to the technical field of adhesives, in particular to a clean board adhesive and a preparation method thereof. Background Art

[0002] Clean board is mainly made of color steel plate, color coated aluminum alloy plate, stainless steel plate, titanium zinc plate as surface material, and rock wool, paper honeycomb, glass magnesium plate, aluminum honeycomb, magnesium oxysulfide, silica rock, gypsum and other core materials. The composite board obtained by bonding and compounding with glue is widely used in clean engineering fields such as electronics, pharmaceuticals, food, biotechnology, medical and precision instrument manufacturing. The glue currently on the market does not take into account the impact of temperature on the actual application process and application effect during the formulation development and design process. For example, in order to ensure faster curing efficiency, the existing glue has a higher reaction activity under high temperature conditions. The active period and open time when used for bonding and compounding of clean board surface materials and core materials are very short, which cannot meet the actual construction application needs under high temperature conditions in summer (above 35°C). For example, a Chinese patent (authorization publication number CN112334553B) discloses a polyurethane composition with long processing time and high strength, which is mainly achieved by synthesizing polyols with different structures to achieve a long open time at room temperature; a Chinese patent (authorization publication number CN101903433B) discloses a two-component polyurethane adhesive for bonding fiber molded parts, which is mainly achieved by combining several polyols and reacting them with isocyanate to ensure a long open time, but it is mainly used for bonding plastic substrates to each other and cannot meet the bonding application requirements of surface materials and core materials in clean panels. Summary of the invention

[0003] In order to solve the above problems, the present invention provides a clean board adhesive, which has a long activity period and open time under high temperature conditions in summer (above 35°C), meets the bonding and processing requirements of the surface material and core material of the clean board, and has high market application value.

[0004] On one hand, the present invention provides a clean board glue, including a main agent and a curing agent. The raw materials for preparing the main agent include at least 20-80 parts of hydroxyl compounds, 1-10 parts of ester plasticizers, 20-60 parts of fillers, and 0.5-5 parts of additives by weight.

[0005] As a preferred technical solution, the raw materials for preparing the main agent include at least 40-60 parts of hydroxyl compounds, 4-9 parts of ester plasticizers, 30-50 parts of fillers, and 2-4 parts of additives, calculated by weight.

[0006] As a preferred technical solution, the hydroxy compound at least includes castor oil and polyether polyol.

[0007] As a preferred technical solution, the hydroxy compound further comprises a small molecule polyol, and the small molecule polyol is selected from at least one of propylene glycol, glycerol, butylene glycol, ethylene glycol, and hexylene glycol, preferably propylene glycol.

[0008] As a preferred technical solution, the mass ratio of castor oil to polyether polyol is (30-40): (10-20).

[0009] As a preferred technical solution, the hydroxyl value of the polyether polyol is 300-400 mgKOH / g, preferably 320-355 mgKOH / g, and the model is polyether polyol HSH305, which is sourced from Nantong Fanbo Chemical Co., Ltd.

[0010] As a preferred technical solution, the mass ratio of the small molecule polyol to the ester plasticizer is (0.5-1.5): (4-6).

[0011] As a preferred technical solution, the ester plasticizer is selected from at least one of fatty acid methyl ester, dibutyl phthalate, dioctyl phthalate, and diisobutyl phthalate, preferably fatty acid methyl ester.

[0012] The adhesive provided by the present invention, by introducing an ester plasticizer, especially the introduced ester plasticizer is fatty acid methyl ester, prolongs the active period and open time of the product at high temperature, and can also increase the tensile shear strength and flat pull strength of the adhesive after application. Further, the present invention controls the addition amount of fatty acid methyl ester in the system to be 4-9 parts by weight, avoids the problem of balancing the open time of the product with the tensile shear strength and flat pull strength when the addition amount of fatty acid methyl ester is too high or too low, and ensures that the comprehensive performance of the product meets the actual application requirements.

[0013] However, the introduction of fatty acid methyl esters leads to a prolonged curing time of the adhesive, and the strength of the adhesive in a short period of time is not enough to meet the actual application needs. During the exploration process, the inventors found that by introducing small molecule polyols, especially propylene glycol, the problem of insufficient strength in a short period of time caused by the introduction of fatty acid methyl esters in the system can be effectively overcome while ensuring a longer activity period and open time, thereby ensuring the tensile shear strength and flat pull strength after application.

[0014] In addition, the present invention constructs a reaction system of castor oil and polyether polyol and small molecule polyol and isocyanate, especially adopts castor oil and polyether polyol with a hydroxyl value of 300-400 mgKOH / g and propylene glycol in combination to react with isocyanate, so that the provided adhesive obtains a suitable processing time while ensuring the bonding strength after curing.

[0015] As a preferred technical solution, the filler is selected from at least one of heavy calcium, active calcium and calcium oxide, preferably a combination of heavy calcium, active calcium and calcium oxide. Preferably, the mass ratio of the heavy calcium, active calcium and calcium oxide is (20-40): (3-8): (3-8), preferably (20-40): 5:5.

[0016] As a preferred technical solution, the particle size of the heavy calcium is 1000-3000 mesh; preferably, the heavy calcium includes heavy calcium ultrafine powder with a particle size of 2000-2500 mesh and heavy calcium fine powder with a particle size of 1000-1500 mesh, and the mass ratio of the heavy calcium ultrafine powder to the heavy calcium fine powder is (0.5-2):1, preferably 1:1.

[0017] As a preferred technical solution, the particle size of the active calcium is 600-1000 mesh, preferably 800 mesh.

[0018] As a preferred technical solution, the auxiliary agent is selected from at least one of a dispersant, a solvent, and a defoaming agent.

[0019] As a preferred technical solution, the dispersant is selected from at least one of polyethylene glycol 1000, polyethylene glycol 2000, polyethylene glycol 4000, and polyethylene glycol 6000, preferably polyethylene glycol 6000.

[0020] As a preferred technical solution, the solvent is DBE (dibasic acid ester).

[0021] As a preferred technical solution, the defoaming agent is a silicone defoaming agent, preferably SGR1832, Xingrui (Shandong).

[0022] As a preferred technical solution, the curing agent is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate, preferably diphenylmethane diisocyanate, Wanhua WANNATE® PM-130.

[0023] As a preferred technical solution, the mass ratio of the main agent to the curing agent is 100:(10-30), preferably 100:20.

[0024] Another aspect of the present invention provides a method for preparing a clean board adhesive, comprising at least the following steps: S1, preparing hydroxy compounds; S2, adding filler to the hydroxy compound and stirring and mixing, adding auxiliary agent and ester plasticizer and stirring and mixing in vacuum to obtain a main agent; S3. When using, stir and mix the main agent and curing agent.

[0025] Preferably, the method for preparing the clean plate adhesive comprises at least the following steps: S1, mixing castor oil, polyether polyol and small molecule polyol under the condition of 500-1000r / min for 10-30min to prepare a hydroxy compound; S2. Add heavy calcium, active calcium and calcium oxide to the hydroxy compound in sequence and stir and mix at 1000-1500r / min for 10-30min. Add dispersant and stir at a vacuum degree of -0.09kpa / cm 2 , stir under vacuum at a speed of 1000-1500 for 0.5-2h, add ester plasticizer, solvent and defoamer at a vacuum degree of -0.09kpa / cm 2 , stirring under vacuum at a rotation speed of 1000-1500 for 10-30 min to obtain the main agent; S3. When using, stir and mix the main agent and curing agent.

[0026] The adhesive provided by the present invention optimizes the particle size coordination and addition amount control of heavy calcium, active calcium and calcium oxide in the system, and under the action of a dispersant and other auxiliary agents, further controls the addition order of each raw material, reduces the difficulty of dispersing heavy calcium, active calcium and calcium oxide in a polymer resin system, and thus ensures the comprehensive performance of the adhesive.

[0027] Beneficial Effects 1. The present invention provides a clean board adhesive, which has a long active period and open time under high temperature conditions in summer (above 35°C), meets the bonding and processing requirements of the surface material and the core material of the clean board, and has a high market application value.

[0028] 2. The adhesive provided by the present invention, by introducing an ester plasticizer, especially the introduced ester plasticizer is fatty acid methyl ester, prolongs the activity period and open time of the product at high temperature, and can also increase the tensile shear strength and flat tensile strength of the adhesive after application.

[0029] 3. The present invention controls the amount of fatty acid methyl ester added in the system to be 4-9 parts by weight, thereby avoiding the problem of too high or too low amount of fatty acid methyl ester added to effectively balance the open time of the product with the tensile shear strength and the flat tensile strength, thereby ensuring that the comprehensive performance of the product meets the actual application requirements.

[0030] 4. The adhesive provided by the present invention, by introducing small molecule polyols, especially propylene glycol, effectively overcomes the problem of insufficient strength in a short period of time caused by the introduction of fatty acid methyl esters in the system while ensuring a longer active period and open time, and ensures the tensile shear strength and flat tensile strength after application.

[0031] 5. The present invention constructs a reaction system of castor oil, polyether polyol, small molecule polyol and isocyanate, especially adopts castor oil, polyether polyol with a hydroxyl value of 300-400 mgKOH / g and propylene glycol in combination with isocyanate to make the provided adhesive obtain a suitable processing time while ensuring the bonding strength after curing. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 The wet (left) and wire-drawn (right) states of the clean sheet adhesive during the open time test of the clean sheet adhesive provided in Example 1.

[0033] Figure 2 The clean sheet adhesive provided in Example 1 is shown before (left) and after (right) the clean sheet adhesive is broken during the tensile shear strength test.

[0034] Figure 3 The state after the color steel plate and the glass magnesium plate are pulled apart (a), the state after the glass magnesium plate and the rock wool are pulled apart (b), and the state before the test (c) in the five-layer structure during the clean plate glue flat tensile strength test provided in Example 1. DETAILED DESCRIPTION

[0035] The sources of the raw materials in the examples and comparative examples of the present invention are shown in Table 1.

[0036] Table 1

[0037] Example 1 Embodiment 1 of the present invention provides a clean board adhesive, including a main agent and a curing agent. The raw materials for preparing the main agent include 50.8 parts of hydroxyl compounds, 5 parts of ester plasticizers, 40 parts of fillers, and 3.1 parts of additives in parts by weight.

[0038] In parts by weight, the hydroxy compound includes 35 parts of castor oil, 15 parts of polyether polyol and 0.8 parts of small molecule polyol.

[0039] The small molecule polyol is propylene glycol.

[0040] The hydroxyl value of the polyether polyol is 320-355 mgKOH / g (polyether polyol HSH305).

[0041] The ester plasticizer is fatty acid methyl ester.

[0042] The filler is a combination of heavy calcium, active calcium and calcium oxide, and the mass ratio of the heavy calcium, active calcium and calcium oxide is 30:5:5.

[0043] The heavy calcium comprises heavy calcium ultrafine powder with a particle size of 2500 meshes and heavy calcium fine powder with a particle size of 1250 meshes, and the mass ratio of the heavy calcium ultrafine powder to the heavy calcium fine powder is 1:1.

[0044] The particle size of the active calcium is 800 meshes.

[0045] In parts by weight, the auxiliary agent includes 1 part of dispersant, 2 parts of solvent and 0.1 part of defoamer.

[0046] The dispersant is polyethylene glycol 6000.

[0047] The solvent is DBE (dibasic acid ester).

[0048] The defoamer is silicone defoamer SGR1832.

[0049] The curing agent is diphenylmethane diisocyanate, WANNATE® PM-130.

[0050] The mass ratio of the main agent to the curing agent is 100:20.

[0051] Embodiment 1 of the present invention provides a method for preparing a clean plate adhesive, comprising the following steps: S1, mixing castor oil, polyether polyol and small molecule polyol under stirring at 800 r / min for 20 min to prepare a hydroxy compound; S2. Add heavy calcium, active calcium and calcium oxide to the hydroxy compound in sequence and stir and mix at 1300r / min for 20min. Add dispersant and set the mixture at a vacuum of -0.09kpa / cm 2 , stirring under vacuum at a speed of 1300r / min for 1h, adding ester plasticizer, solvent and defoamer at a vacuum degree of -0.09kpa / cm 2 , stirring under vacuum at a rotation speed of 1300 r / min for 20 min to obtain the main agent; S3. When using, stir and mix the main agent and curing agent.

[0052] Comparative Example 1 Comparative Example 1 of the present invention provides a clean plate glue and a preparation method thereof, and its specific implementation manner is the same as that of Example 1, except that the fatty acid methyl ester is replaced by phosphoric acid.

[0053] Comparative Example 2 Comparative Example 2 of the present invention provides a clean board glue and a preparation method thereof, and its specific implementation manner is the same as that of Example 1, except that the fatty acid methyl ester is replaced by dibutyl phthalate (DBP).

[0054] Comparative Example 3 Comparative Example 3 of the present invention provides a clean board glue and a preparation method thereof, and its specific implementation manner is the same as that of Example 1, except that the polyether polyol HSH305 is replaced by polyether polyol HSH330N (hydroxyl value is 33-37 mgKOH / g).

[0055] Comparative Example 4 Comparative Example 4 of the present invention provides a clean board glue and a preparation method thereof, and its specific implementation manner is the same as that of Example 1, except that the castor oil is replaced by a mixture of castor oil and soybean oil in a mass ratio of 9:1.

[0056] Comparative Example 5 Comparative Example 5 of the present invention provides a clean board glue and a preparation method thereof, and its specific implementation method is the same as Example 1, except that, by weight, the raw materials for preparing the main agent include 50.8 parts of hydroxyl compounds, 10 parts of ester plasticizers, 40 parts of fillers, and 3.1 parts of additives.

[0057] Comparative Example 6 Comparative Example 6 of the present invention provides a clean board glue and a preparation method thereof, and its specific implementation method is the same as Example 1, except that, by weight, the raw materials for preparing the main agent include 50.8 parts of hydroxyl compounds, 3 parts of ester plasticizers, 40 parts of fillers, and 3.1 parts of additives.

[0058] Comparative Example 7 Comparative Example 7 of the present invention provides a clean board glue and a preparation method thereof, and its specific implementation method is the same as that of Example 1, except that, by weight, the raw materials for preparing the main agent include 50 parts of hydroxyl compounds, 5 parts of ester plasticizers, 40 parts of fillers, and 3.1 parts of additives; by weight, the hydroxyl compounds include 35 parts of castor oil and 15 parts of polyether polyols.

[0059] Comparative Example 8 Comparative Example 8 of the present invention provides a clean plate glue and a preparation method thereof, and its specific implementation manner is the same as that of Example 1, except that, in parts by weight, the propylene glycol is replaced by glycerol.

[0060] Performance Testing 1. Test Example 1: The activity period of the clean board adhesive provided in Comparative Examples 1-8 at 35°C and 40°C is determined as the time when obvious resistance appears when stirring after the main agent and curing agent in each embodiment are evenly mixed. The test results are shown in Table 2.

[0061] 2. Test the open time of the clean plate adhesive provided in Example 1 and Comparative Examples 1-8 at 35°C and 40°C. Specifically, after the main agent and curing agent in each example are mixed evenly, they are coated on the surface of the substrate (aluminum sheet), and the adhesive film state changes from wet to wire drawing state (the wet and wire drawing states of the clean plate adhesive provided in Example 1 refer to Figure 1 ), then the opening time is judged to be over, and the test results are shown in Table 2.

[0062] 3. According to the national standard GB / T7124 / 2008, the tensile shear strength of the clean plate glue provided in Example 1 and Comparative Examples 1-8 for aluminum sheets and aluminum sheets was tested after curing for 7 days (the glue application amount was 200g / m 2 ), the test results are shown in Table 2, when the tensile shear strength of the clean plate adhesive provided in Example 1 is tested, the states before and after breaking are shown in Table 2. Figure 2 .

[0063] 4. According to the national standard GB / T1452 / 2018, the clean plate glue provided in Example 1 and Comparative Examples 1-8 was used for the flat tensile strength of the five-layer structure (color steel plate-clean plate glue-glass magnesium plate-clean plate glue-rock wool-clean plate glue-glass magnesium plate-clean plate glue-color steel plate) after curing for 1 day (the glue application amount was 280±20g / m 2 ), the test results are shown in Table 2, and when the flat tensile strength of the clean plate adhesive provided in Example 1 is tested, the states before and after breaking are shown in Table 2. Figure 3 .

[0064] Table 2

Claims

1. A clean board glue, It is characterized in that The invention comprises a main agent and a curing agent. The raw materials for preparing the main agent include at least 40-60 parts of hydroxyl compounds, 4-9 parts of ester plasticizers, 30-50 parts of fillers and 2-4 parts of auxiliary agents by weight. The hydroxyl compound is a combination of castor oil, polyether polyol and small molecule polyol. The hydroxyl value of the polyether polyol is 300-400 mgKOH / g. The small molecule polyol is propylene glycol. The mass ratio of the small molecule polyol to the ester plasticizer is (0.5-1.5):(4-6). The ester plasticizer is fatty acid methyl ester.

2. The clean board adhesive according to claim 1, It is characterized in that The hydroxyl value of the polyether polyol is 320-355 mgKOH / g.

3. The clean board glue according to claim 2, It is characterized in that The mass ratio of castor oil to polyether polyol is (30-40):(10-20).

4. The clean board adhesive according to claim 3, It is characterized in that The filler is selected from at least one of heavy calcium, active calcium and calcium oxide.

5. The clean board adhesive according to claim 4, It is characterized in that The filler is a combination of heavy calcium, active calcium and calcium oxide, and the mass ratio of the heavy calcium, active calcium and calcium oxide is (20-40): (3-8): (3-8).

6. The clean board adhesive according to claim 5, It is characterized in that The heavy calcium includes heavy calcium ultrafine powder with a particle size of 2000-2500 meshes and heavy calcium fine powder with a particle size of 1000-1500 meshes.

7. The clean board adhesive according to claim 6, It is characterized in that The auxiliary agent is selected from at least one of a dispersant, a solvent and a defoamer.

8. The clean board adhesive according to claim 7, It is characterized in that The dispersant is selected from at least one of polyethylene glycol 1000, polyethylene glycol 2000, polyethylene glycol 4000 and polyethylene glycol 6000.

9. The clean board adhesive according to claim 8, It is characterized in that The curing agent is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.

10. A method for preparing the clean board adhesive according to any one of claims 1 to 9, It is characterized in that At least the following steps are included: S1, preparing hydroxy compounds; S2, adding filler to the hydroxy compound and stirring and mixing, adding auxiliary agent and ester plasticizer and stirring and mixing in vacuum to obtain a main agent; S3. When using, stir and mix the main agent and curing agent.

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