Clean-panel adhesive and preparation method therefor

Abstract

The present invention relates to the technical field of adhesives, and in particular relates to a clean-panel adhesive and a preparation method therefor. The clean-panel adhesive comprises a main agent and a curing agent. The main agent at least comprises, in parts by weight, the raw preparation materials of 40-60 parts of a hydroxyl compound, 4-9 parts of an ester plasticizer, 30-50 parts of a filler and 2-4 parts of an auxiliary agent. The hydroxyl compound at least comprises castor oil, a polyether polyol and a low‑molecular‑weight polyol. The hydroxyl value of the polyether polyol is 300 to 400 mgKOH / g and the low‑molecular‑weight polyol is propylene glycol. The mass ratio of the low‑molecular‑weight polyol to the ester plasticizer is (0.5-1.5):(4-6); the ester plasticizer is a fatty acid methyl ester. The adhesive has a relatively long pot life and open time under high-temperature conditions (35°C or more) in summer, meets bonding and processing requirements for a face material and a core material in a clean panel, and has a high market application value.

Description

Clean plate glue and preparation method thereof TECHNICAL FIELD

[0001] The present application relates to the technical field of adhesives, in particular to a clean plate glue and a preparation method thereof. BACKGROUND

[0002] Clean plate is mainly composed of color steel plate, color-coated aluminum alloy plate, stainless steel plate and titanium-zinc plate as surface material, and rock wool, paper honeycomb, glass magnesium plate, aluminum honeycomb, magnesium sulfate, silicon rock and gypsum as core material, which are bonded and combined by glue, and widely used in clean engineering fields such as electronics, pharmaceuticals, food, biotechnology, medical treatment and precision instrument manufacturing. The glue on the market does not consider the influence of temperature on the actual application process and application effect in the formula development and design process. For example, in order to ensure faster curing efficiency, the existing glue has high reactivity under high temperature conditions, and the activity period and open time are very short when used for bonding and combining the surface material and core material of the clean plate, which cannot meet the actual construction application requirements under high temperature conditions (above 35℃) in summer. For example, Chinese patent (authorized publication number CN112334553B) discloses a polyurethane composition with long processing time and high strength, which mainly realizes long open time at room temperature by synthesizing polyols with different structures; Chinese patent (authorized publication number CN101903433B) discloses a two-component polyurethane adhesive for bonding fiber molded parts, which mainly ensures long open time by combining several polyols and reacting with isocyanate, but it is mainly used for the mutual bonding of plastic substrates, and cannot meet the bonding application requirements of the surface material and core material of the clean plate. SUMMARY

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

[0004] In one aspect, the present application provides a clean plate glue, which comprises a main agent and a curing agent, and the preparation raw materials of the main agent at least include 20-80 parts by weight of hydroxyl compounds, 1-10 parts by weight of ester plasticizer, 20-60 parts by weight of filler and 0.5-5 parts by weight of auxiliary agent.

[0005] As a preferred technical solution, the preparation raw materials of the main agent at least include 40-60 parts by weight of hydroxyl compounds, 4-9 parts by weight of ester plasticizer, 30-50 parts by weight of filler and 2-4 parts by weight of auxiliary agent.

[0006] As a preferred technical solution, the hydroxyl compounds at least include castor oil and polyether polyol.

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

[0008] As a preferred technical solution, the mass ratio of the castor oil to the 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, and preferably 320-355 mgKOH / g, and the model is polyether polyol HSH305 from Nantong Fange 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, diisobutyl phthalate, and preferably fatty acid methyl ester.

[0012] The adhesive provided by the present application prolongs the active period and open time of the product at high temperature by introducing the ester plasticizer, especially the introduced ester plasticizer is fatty acid methyl ester, and can also increase the tensile shear strength and flat tensile strength after application of the adhesive. Further, by controlling the addition amount of fatty acid methyl ester in the system to be 4-9 parts by weight, the problem of imbalance between the open time and the tensile shear strength and flat tensile strength of the product caused by excessive or insufficient addition amount of fatty acid methyl ester is avoided, and the comprehensive performance of the product is ensured to meet the actual application requirements.

[0013] However, the introduction of fatty acid methyl ester leads to the prolongation of the curing time of the adhesive, and the strength of the adhesive in a short time is insufficient to meet the actual application requirements. The inventors found in the exploration process that by introducing a small molecule polyol, especially propylene glycol, the problem of insufficient strength in a short time caused by the introduction of fatty acid methyl ester in the system is effectively overcome under the condition of ensuring a longer active period and open time, and the tensile shear strength and flat tensile strength after application are ensured.

[0014] In addition, by constructing the reaction system of castor oil and polyether polyol and small molecule polyol and isocyanate, especially by using castor oil combined with polyether polyol with a hydroxyl value of 300-400 mgKOH / g and propylene glycol to react with isocyanate, the adhesive provided by the present application 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, 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 superfine 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 superfine powder and 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 dispersing agent, a solvent and a defoaming agent.

[0019] As a preferred technical solution, the dispersing agent 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 (divalent acid ester).

[0021] As a preferred technical solution, the defoaming agent is an organic silicon defoaming agent, preferably SGR1832, Xingge (Shandong).

[0022] As a preferred technical solution, the curing agent is selected from at least one of toluene diisocyanate, diphenyl methane diisocyanate, hexamethylene diisocyanate and isoflurone diisocyanate, preferably diphenyl methane diisocyanate, Wanhua

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

[0024] Another aspect of the present application provides a preparation method of clean plate glue, at least comprising the following steps:

[0025] S1, preparing a hydroxyl compound;

[0026] S2, adding a filler to the hydroxyl compound and stirring and mixing, adding an auxiliary agent and an ester plasticizer and vacuum stirring and mixing to obtain a main agent;

[0027] S3, when used, the main agent and the curing agent are stirred and mixed to obtain.

[0028] Preferably, the preparation method of the clean plate adhesive comprises the following steps:

[0029] S1, castor oil, polyether polyol and small molecule polyol are stirred and mixed under the condition of 500-1000 r / min for 10-30 min to prepare a hydroxyl compound;

[0030] S2, heavy calcium, active calcium and calcium oxide are sequentially added to the hydroxyl compound, and stirred and mixed under the condition of 1000-1500 r / min for 10-30 min, a dispersing agent is added, and vacuum stirring is carried out under the condition of a vacuum degree of-0.09 kpa / cm 2 , a rotation speed of 1000-1500 r / min for 0.5-2 h, an ester plasticizer, a solvent and a defoaming agent are added, and vacuum stirring is carried out under the condition of a vacuum degree of-0.09 kpa / cm 2 , a rotation speed of 1000-1500 r / min for 10-30 min to obtain a main agent;

[0031] S3, when used, the main agent and the curing agent are stirred and mixed to obtain the adhesive.

[0032] The adhesive provided by the application can further control the adding sequence of each raw material, reduce the dispersion difficulty of heavy calcium, active calcium and calcium oxide in the polymer resin system, and thus ensure the comprehensive performance of the adhesive. Advantages

[0033] 1. The clean plate adhesive provided by the application has a long active period and open time under high-temperature conditions in summer (above 35 DEG C), meets the bonding and processing requirements of the surface material and core material in the clean plate, and has high market application value.

[0034] 2. The adhesive provided by the application can prolong the active period and open time of the product under high temperature by introducing an ester plasticizer, especially a fatty acid methyl ester, and can also increase the tensile shear strength and flat tensile strength after application of the adhesive.

[0035] 3. The application controls the adding amount of the fatty acid methyl ester in the system to be 4-9 parts by weight, avoids the problem that the adding amount of the fatty acid methyl ester is too high or too low to effectively balance the open time and the tensile shear strength and flat tensile strength of the product, and ensures that the comprehensive performance of the product meets the actual application requirements.

[0036] 4、The adhesive provided by the present application effectively overcomes the problem of insufficient strength in a short time caused by the introduction of fatty acid methyl ester in the system under the condition of ensuring a longer active period and open time, ensures the tensile shear strength and flat tensile strength after application.

[0037] 5、The present application constructs a reaction system of castor oil, polyether polyol and small molecule polyol and isocyanate, especially uses castor oil, polyether polyol with a hydroxyl value of 300-400 mgKOH / g and propylene glycol combined with isocyanate reaction, so that the provided adhesive obtains suitable processing time while ensuring the bonding strength after curing. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 is the wet (left) and wire drawing (right) state of the clean plate adhesive during the open time test of the clean plate adhesive provided by Example 1.

[0039] Figure 2 is the state of the clean plate adhesive before (left) and after (right) being pulled off during the tensile shear strength test of the clean plate adhesive provided by Example 1.

[0040] Figure 3 is the state after being pulled off between the color steel plate and the glass magnesium plate (a), the state after being pulled off between the glass magnesium plate and the rock wool (b), and the state before testing (c) in the five-layer structure during the flat tensile strength test of the clean plate adhesive provided by Example 1. DETAILED DESCRIPTION

[0041] The sources of the raw materials in the examples and comparative examples of the present application are shown in Table 1.

[0042] Table 1

[0043] Example 1

[0044] Example 1 of the present application provides a clean plate adhesive, which comprises a main agent and a curing agent, and the preparation raw materials of the main agent include 50.8 parts of a hydroxyl compound, 5 parts of an ester plasticizer, 40 parts of a filler and 3.1 parts of an auxiliary agent by weight.

[0045] The hydroxyl compound includes 35 parts of castor oil, 15 parts of polyether polyol and 0.8 parts of small molecule polyol by weight.

[0046] The small molecule polyol is propylene glycol.

[0047] The polyether polyol has a hydroxyl value of 320-355 mgKOH / g (polyether polyol HSH305).

[0048] The ester plasticizer is fatty acid methyl ester.

[0049] The filler is a combination of heavy calcium, active calcium and calcium oxide.

[0050] The heavy calcium includes heavy calcium superfine powder with a particle size of 2500 mesh and heavy calcium fine powder with a particle size of 1250 mesh, and the mass ratio of the heavy calcium superfine powder and the heavy calcium fine powder is 1:1.

[0051] The active calcium has a particle size of 800 mesh.

[0052] The auxiliary agent includes 1 part of a dispersant, 2 parts of a solvent and 0.1 part of an antifoaming agent by weight.

[0053] The dispersant is polyethylene glycol 6000.

[0054] The solvent is DBE (divalent acid ester).

[0055] The antifoaming agent is silicone antifoaming agent SGR1832.

[0056] The curing agent is diphenyl methane diisocyanate,

[0057] The mass ratio of the main agent and the curing agent is 100:20.

[0058] The embodiment 1 of the present application provides a preparation method of clean plate glue, comprising the following steps:

[0059] S1, castor oil, polyether polyol and small molecule polyol are stirred and mixed at 800 r / min for 20 min to prepare a hydroxyl compound;

[0060] S2, heavy calcium, active calcium and calcium oxide are sequentially added to the hydroxyl compound, and stirred and mixed at 1300 r / min for 20 min, a dispersant is added, vacuum stirring is carried out at a vacuum degree of-0.09 kpa / cm 2 , and a rotating speed of 1300 r / min for 1 h, ester plasticizer, solvent and antifoaming agent are added, vacuum stirring is carried out at a vacuum degree of-0.09 kpa / cm 2 , and a rotating speed of 1300 r / min for 20 min to obtain the main agent;

[0061] S3, when used, the main agent and the curing agent are stirred and mixed to obtain the clean plate glue.

[0062] Comparative example 1

[0063] The comparative example 1 of the present application provides a clean plate glue and a preparation method thereof, and the specific embodiment is the same as that of the embodiment 1, and the difference lies in that the fatty acid methyl ester is replaced by phosphoric acid.

[0064] Comparative example 2

[0065] The comparative example 2 of the present application provides a clean board adhesive and a preparation method thereof, and the specific embodiment is the same as that of the example 1, except that the fatty acid methyl ester is replaced by dibutyl phthalate (DBP).

[0066] Comparative example 3

[0067] The comparative example 3 of the present application provides a clean board adhesive and a preparation method thereof, and the specific embodiment is the same as that of the example 1, except that the polyether polyol HSH305 is replaced by polyether polyol HSH330N (hydroxyl value is 33-37 mgKOH / g).

[0068] Comparative example 4

[0069] The comparative example 4 of the present application provides a clean board adhesive and a preparation method thereof, and the specific embodiment is the same as that of the example 1, except that the castor oil is replaced by a mixture of castor oil and soybean oil with a mass ratio of 9:1.

[0070] Comparative example 5

[0071] The comparative example 5 of the present application provides a clean board adhesive and a preparation method thereof, and the specific embodiment is the same as that of the example 1, except that the preparation raw materials of the main agent include 50.8 parts of hydroxyl compound, 10 parts of ester plasticizer, 40 parts of filler, and 3.1 parts of auxiliary agent by weight.

[0072] Comparative example 6

[0073] The comparative example 6 of the present application provides a clean board adhesive and a preparation method thereof, and the specific embodiment is the same as that of the example 1, except that the preparation raw materials of the main agent include 50.8 parts of hydroxyl compound, 3 parts of ester plasticizer, 40 parts of filler, and 3.1 parts of auxiliary agent by weight.

[0074] Comparative example 7

[0075] The comparative example 7 of the present application provides a clean board adhesive and a preparation method thereof, and the specific embodiment is the same as that of the example 1, except that the preparation raw materials of the main agent include 50 parts of hydroxyl compound, 5 parts of ester plasticizer, 40 parts of filler, and 3.1 parts of auxiliary agent by weight, and the hydroxyl compound includes 35 parts of castor oil and 15 parts of polyether polyol by weight.

[0076] Comparative example 8

[0077] The comparative example 8 of the present application provides a clean board adhesive and a preparation method thereof, and the specific embodiment is the same as that of the example 1, except that the propylene glycol is replaced by glycerol by weight.

[0078] Performance test

[0079] 1. The active period of the clean panel adhesive provided in Example 1, Comparative Examples 1-8 at 35°C and 40°C was tested. The time when the mixing of the main agent and curing agent in each example was uniform and the stirring resistance was obvious was determined as the active period. The test results are shown in Table 2.

[0080] 2. The open time of the clean panel adhesive provided in Example 1, Comparative Examples 1-8 at 35°C and 40°C was tested. After the mixing of the main agent and curing agent in each example was uniform, the adhesive film was coated on the surface of the substrate (aluminum sheet). When the state of the adhesive film changed from wet to stringy (see Figure 1 for the wet and stringy states of the clean panel adhesive provided in Example 1), the open time was determined to be over. The test results are shown in Table 2.

[0081] 3. The tensile shear strength of the clean panel adhesive provided in Example 1, Comparative Examples 1-8 for aluminum sheet and aluminum sheet was tested according to the national standard GB / T7124 / 2008, with 7 days of curing. The adhesive amount was 200 g / m 2 . The test results are shown in Table 2. When the tensile shear strength of the clean panel adhesive provided in Example 1 was tested, the states before and after breaking were shown in Figure 2.

[0082] 4. The flat tensile strength of the clean panel adhesive provided in Example 1, Comparative Examples 1-8 for a five-layer structure (color steel plate-clean panel adhesive-glass magnesium plate-clean panel adhesive-rock wool-clean panel adhesive-glass magnesium plate-clean panel adhesive-color steel plate) was tested according to the national standard GB / T1452 / 2018, with 1 day of curing. The adhesive amount was 280±20 g / m 2 . The test results are shown in Table 2. When the flat tensile strength of the clean panel adhesive provided in Example 1 was tested, the states before and after breaking were shown in Figure 3.

[0083] Table 2

Claims

1. A cleanroom board adhesive, characterized in that, The product comprises a main agent and a curing agent. By weight, the main agent is prepared from raw materials comprising at least 40-60 parts of a hydroxyl compound, 4-9 parts of an ester plasticizer, 30-50 parts of a filler, and 2-4 parts of an auxiliary agent. The hydroxyl compound is a combination of castor oil, polyether polyol, and small molecule polyol. The polyether polyol has a hydroxyl value of 300-400 mg KOH / 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 cleanroom board adhesive according to claim 1, characterized in that, The hydroxyl value of the polyether polyol is 320-355 mg KOH / g.

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

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

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

6. The cleanroom board adhesive according to claim 5, characterized in that, The superphosphate includes superphosphate ultrafine powder with a particle size of 2000-2500 mesh and superphosphate fine powder with a particle size of 1000-1500 mesh.

7. The cleanroom board adhesive according to claim 6, characterized in that, The additive is selected from at least one of dispersants, solvents, and defoamers.

8. The cleanroom board adhesive according to claim 7, 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 cleanroom board adhesive according to claim 8, characterized in that, The curing agent is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isoflurone diisocyanate.

10. A method for preparing the cleanroom board adhesive according to any one of claims 1-9, characterized in that, At least the following steps are included: S1. Preparation of hydroxyl compounds; S2. Add filler to the hydroxyl compound and stir to mix. Add auxiliaries and ester plasticizers and stir under vacuum to obtain the main agent. S3. When using, simply mix the main agent and the curing agent.

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