Waterproof adhesive composition and preparation method thereof

Abstract

The invention relates to the field of adhesive materials, in particular to a waterproof adhesive composition and a preparation method thereof, and more particularly relates to a heat-activated waterproof adhesive composition. The invention provides a waterproof adhesive composition. The waterproof adhesive composition comprises thermoplastic polyurethane resin, thermoplastic polyester resin, a curing agent, terpene resin and petroleum resin. According to the waterproof adhesive composition disclosed by the invention, through mutual cooperation of all the components, the initial adhesion of the composition is improved, so that the waterproof adhesive composition can be suitable for more polar base materials, meanwhile, the wettability and the permanent adhesion can be improved, meanwhile, the waterproof adhesive composition can prevent permeation of various liquids, and the waterproof adhesive composition is relatively good in weather resistance and chemical resistance; the construction time of the hot melt adhesive is shorter, and the printing property is good.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of adhesive materials, in particular, to a waterproof adhesive composition and a preparation method thereof, more particularly, to a heat-activated waterproof adhesive composition. BACKGROUND

[0002] With the rapid development of electronic devices towards miniaturization, integration, and portability, and the extension of application scenarios to outdoor, underwater, high-humidity salt spray, and other complex environments, waterproof sealing has become a core requirement to ensure the reliability and service life of electronic components. As a key protective material, waterproof adhesive compositions form a dense protective film on the surface and gaps of components, achieving waterproof, moisture-proof, insulation, corrosion resistance, and other functions, and are widely used in consumer electronics, automotive electronics, industrial equipment, medical devices, new energy, and other fields. The performance of the waterproof adhesive compositions directly determines the environmental adaptability and safety and stability of the equipment.

[0003] Acrylate pressure-sensitive adhesives are currently the preferred choice for waterproofing electronic products on the market due to their shorter application time and good printability compared to hot melt adhesives. However, acrylate waterproofing adhesives have poor weather resistance and chemical resistance, which can lead to insufficient protection of electronic products in extreme harsh environments, causing short-circuit failure of electronic products.

[0004] Therefore, there is a need for a waterproof adhesive composition that has good weather resistance and chemical resistance, and at the same time has a shorter application time and good printability of hot melt adhesives. SUMMARY

[0005] The present application is made in view of the above-mentioned problems, and aims to provide a waterproof adhesive composition that has good weather resistance and chemical resistance, and at the same time has a shorter application time and good printability of hot melt adhesives.

[0006] To achieve the above-mentioned purpose, in a first aspect, the present application provides a waterproof adhesive composition, comprising: a thermoplastic polyurethane resin, a thermoplastic polyester resin, a curing agent, a terpene resin, and a petroleum resin.

[0007] The waterproof adhesive composition of the present application improves the initial adhesion of the composition through the mutual cooperation of the components, making it applicable to more polar substrates, while improving wetting and holding power. At the same time, it can prevent the penetration of various liquids, has good weather resistance and chemical resistance, and has a shorter application time and good printability of hot melt adhesives.

[0008] In some specific embodiments, the thermoplastic polyester resin comprises 5-10% by mass of the entire waterproof adhesive composition. For example, it can comprise 5%, 6%, 7%, 8%, 9%, 10% by mass of the entire composition. For example, 10-20 g of the thermoplastic polyester resin can be contained per 100 g of the composition of the present application.

[0009] Further, the thermoplastic polyester can be selected from one or more of the following classes: IROSTIC S 6148, IROSTIC S 8743, IROSTIC S 7614, IROSTIC S 9815, Lubrizol 5703, or Lubrizol 5715.

[0010] In some specific embodiments, the thermoplastic polyester resin comprises 5-10% by mass of the entire waterproof adhesive composition. For example, it can comprise 5%, 6%, 7%, 8%, 9%, 10% by mass of the entire composition. For example, 10-20 g of the thermoplastic polyester resin can be contained per 100 g of the composition of the present application.

[0011] Further, the thermoplastic polyester can be selected from one or more of the following classes: ES-420, ES-660, ES-680, ES-901, GK-103, GK-270, or GK-240.

[0012] In some specific embodiments, the terpene resin comprises 5-9% by mass of the entire waterproof adhesive composition. For example, it can comprise 5%, 6%, 7%, 8%, 9% by mass of the entire composition. For example, 5-9 g of the terpene resin can be contained per 100 g of the composition of the present application.

[0013] In some specific embodiments, the petroleum resin comprises 4-7.5% by mass of the entire waterproof adhesive composition. For example, it can comprise 4%, 5%, 6%, 7%, 7.5% by mass of the entire composition. For example, 4-7.5 g of the petroleum resin can be contained per 100 g of the composition of the present application.

[0014] In some specific embodiments, the curing agent comprises 0.5-1% by mass of the entire waterproof adhesive composition. For example, it can comprise 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1% by mass of the entire composition. For example, 0.5-1 g of the curing agent can be contained per 100 g of the composition of the present application.

[0015] Further, the curing agent includes a latent isocyanate curing agent.

[0016] Furthermore, the latent isocyanate curing agent is selected from one or more of the following types: TPA-B80X, SBN-70D, FBN11-70B, MF-K60X, or TKA-B75S.

[0017] Furthermore, the waterproof adhesive composition does not include acrylic resins.

[0018] In some specific embodiments, the waterproof adhesive composition further includes one or more of a diluent, coupling agent, defoamer, leveling agent, filler, acid catalyst, or antioxidant.

[0019] In some specific embodiments, the diluent accounts for 50%-60% of the total mass of the waterproof adhesive composition. For example, it can account for 50%, 55%, or 60% of the total mass of the composition. For example, each 100g of the composition of the present invention may contain 10g-20g of diluent.

[0020] Furthermore, the diluent may be selected from one or more of the following: Diethylene glycol phenyl ether acetate, diethylene glycol butyl ether acetate, a mixture of dicarboxylic acid esters, hexadecyl alcohol ester, butyl acetate, diethylene glycol benzoate, propylene glycol monomethyl ether, or N-methylpyrrolidone.

[0021] In some specific embodiments, the coupling agent accounts for 0.5%-1% of the total mass of the waterproof adhesive composition. For example, it can account for 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1% of the total mass of the composition. For example, each 100g of the composition of the present invention may contain 0.5g-1g of coupling agent.

[0022] Furthermore, coupling agents include silane coupling agents.

[0023] Furthermore, the silane coupling agent is selected from one or more of the following: KH550, KH560, or KH570.

[0024] In some specific embodiments, the defoamer accounts for 0.5%-1% of the total mass of the waterproof adhesive composition. For example, it may account for 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1% of the total mass of the composition. For example, 0.5g-1g of defoamer may be contained in every 100g of the composition of the present invention.

[0025] Furthermore, defoamers include silicone-based defoamers.

[0026] Furthermore, the silicone-based defoamer is selected from one or more of the following categories: BYK-066N, BYK-1810, BYK-1815, TECH-3868, TECH-3904, TEGO-904W, or TEGO-810.

[0027] In some specific embodiments, the leveling agent accounts for 0.5%-1% of the total mass of the waterproof adhesive composition. For example, it may account for 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1% of the total mass of the composition. For example, 100g of the composition of the present invention may contain 0.5g-1g of leveling agent.

[0028] Furthermore, leveling agents include silicone-based leveling agents.

[0029] Furthermore, the silicone leveling agent is selected from one or more of the following categories: TECH-2768, TECH-2769, BYK-333, BYK-322, BYK-320, TEGO-2300, or TEGO-482.

[0030] In some specific embodiments, the filler accounts for 1%-2% of the total mass of the waterproof adhesive composition. For example, it may account for 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2% of the total mass of the composition. For example, 1g-2g of filler may be contained in every 100g of the composition of the present invention.

[0031] Furthermore, the filler includes hydrophobic fumed silica.

[0032] Furthermore, the hydrophobic fumed silica is selected from one or more of the following types: TS-610, TS-720, M21S, or M210S.

[0033] In some specific embodiments, the acid catalyst accounts for 0.5%-1% of the total mass of the waterproof adhesive composition. For example, it can account for 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1% of the total mass of the composition. For example, 100g of the composition of the present invention may contain 0.5g-1g of acid catalyst.

[0034] Furthermore, acid catalysts include sulfonate acid catalysts.

[0035] Furthermore, the sulfonate acid catalyst is selected from one or more of the following: NACURE-2500 or TECH-8500N.

[0036] In some specific embodiments, the antioxidant accounts for 0.05%-0.08% of the total mass of the waterproof adhesive composition. For example, it may account for 0.05%, 0.06%, 0.07%, or 0.08% of the total mass of the composition. For example, 100g of the composition of the present invention may contain 0.05g-0.08g of antioxidant.

[0037] Furthermore, antioxidants include phenolic antioxidants.

[0038] Furthermore, phenolic antioxidants are selected from one or more of the following categories: Inganox1098, Inganox1010, Inganox1076, AT-168, or LOWINOX1790.

[0039] Secondly, this application provides an application of the above-mentioned waterproof adhesive composition in the preparation of waterproof adhesives.

[0040] Furthermore, the waterproof adhesive is a waterproof adhesive for electronic products.

[0041] Thirdly, the present invention provides a method for preparing a waterproof adhesive, comprising the following steps: Thermoplastic polyurethane resin, thermoplastic polyester resin, terpene resin and petroleum resin are mixed at 60℃~80℃ and 100~150rpm for the first stirring until completely dissolved. Add the remaining components and stir a second time at 20℃~25℃ and 80~150rpm until completely dissolved to obtain the waterproof adhesive precursor; and The waterproof adhesive precursor is ground, dispersed, and filtered to obtain the waterproof adhesive.

[0042] In some specific implementations, thermoplastic polyurethane resin, thermoplastic polyester resin, terpene resin, and petroleum resin are mixed at 60°C and 150 rpm and stirred for the first time until completely dissolved.

[0043] In some specific implementations, the remaining components are added, and the mixture is further stirred a second time at 20°C and 80-120 rpm until completely dissolved to obtain the waterproof adhesive precursor. In some specific implementations, the remaining components include one or more of the following: diluent, curing agent, coupling agent, defoamer, leveling agent, filler, acid catalyst, or antioxidant.

[0044] In some specific implementations, the grinding parameters are 40μm / 20μm; rotation speed 200-400rpm; and roller temperature 20-25℃. Attached Figure Description

[0045] Figure 1 This is a schematic diagram of the peel strength test. Detailed Implementation

[0046] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0047] Unless otherwise specified, all embodiments and optional embodiments of this application may be combined to form new technical solutions.

[0048] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0049] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the method may also include step (c), indicating that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0050] Unless otherwise specified, the terms used in this application have the common meanings as commonly understood by those skilled in the art.

[0051] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit this disclosure. When used herein, the singular forms “a,” “an,” and “the” are also intended to include the plural forms unless the context clearly indicates otherwise. It should also be understood that the terms “comprise” and / or “comprising,” when used in this specification, identify the presence of the stated features, integers, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups. When used herein, the term “and / or” includes any and all combinations of the associated listed items.

[0052] definition "Thermoplastic polyurethane" refers to a linear block copolymer that is polymerized by the reaction of diisocyanate, macromolecular polyol and chain extender. It is an elastomer that can be plasticized by heating and dissolved by solvent.

[0053] "Thermoplastic polyester" refers to a block copolymer that consists of alternating crystalline hard segments and amorphous soft segments, and has the property of being plasticized by heating.

[0054] "Petroleum resin" refers to a type of thermoplastic, low-molecular-weight hydrocarbon resin made from petroleum cracking byproducts (C5, C9, etc.) through pretreatment, polymerization, distillation, and other processes.

[0055] "Dicrate mixture" refers to a colorless, transparent, and nearly odorless liquid mixture composed of three dimethyl dicarboxylic acids in a specific ratio. Its standard composition typically includes: dimethyl succinate, dimethyl glutarate, and dimethyl adipate.

[0056] "Room temperature" refers to 20℃.

[0057] Example The following describes embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.

[0058] Example 1 (1) Add 300g of thermoplastic polyurethane resin IROSTIC S 8743 (Huntsman), 100g of thermoplastic polyester resin ES-660 (SK Chemicals), 120g of terpene resin (Arakawa Chemicals), 80g of petroleum resin (Eastman), and 900g of diethylene glycol butyl ether acetate (Sinopharm) to the reactor and stir at 500rpm and 60℃ for 8h.

[0059] (2) After cooling, add 20g of filler TS-720 (Cabot), 15g of silane coupling agent KH-560 (Longcheng Organosilicon), 10g of curing agent TKA-B75S (Dornex), 15g of defoamer BYK-066N (BYK), 30g of leveling agent BYK-320 (BYK), 15g of acid catalyst NACURE-2500 (King's Chemical), and 1g of antioxidant Ingonox1010 (BASF) to (1) and stir at room temperature for 30min.

[0060] (3) Stop stirring and grind the mixture in (2) thoroughly with a three-roll mill.

[0061] (4) Filter the mixture in (3) and finally seal it in a jar.

[0062] Example 2 (1) Add 350g of thermoplastic polyurethane resin IROSTIC S 7614 (Huntsman), 150g of thermoplastic polyester resin ES-680 (SK Chemicals), 100g of terpene resin (Arakawa Chemicals), 100g of petroleum resin (Eastman), and 950g of diethylene glycol phenyl ether acetate (Sinopharm) to the reactor and stir at 500rpm and 60℃ for 8h.

[0063] (2) After cooling, add 18g of filler M210S (produced by Guangyue New Materials), 17g of silane coupling agent KH-570 (produced by Longcheng Organosilicon), 15g of curing agent SBN-70D (produced by Donade), 18g of defoamer BYK-1815 (produced by BYK), 35g of leveling agent BYK-333 (produced by BYK), 16g of acid catalyst NACURE-2500 (produced by King's Chemical), and 1.4g of antioxidant Ingonox1098 (produced by BASF) to (1) in sequence and stir at room temperature for 30min.

[0064] (3) Stop stirring and grind the mixture in (2) thoroughly with a three-roll mill.

[0065] (4) Filter the mixture in (3) and finally seal it in a jar.

[0066] Example 3 (1) Add 250g of thermoplastic polyurethane resin Lubrizol 5715 (Huntsman), 170g of thermoplastic polyester resin GK-270 (Toyobo), 140g of terpene resin (Arakawa Chemical), 100g of petroleum resin (Eastman), and 1000g of dicarboxylic acid ester mixture (Kukyaku) to the reactor and stir at 500rpm and 60℃ for 8h.

[0067] (2) After cooling, add 20g of filler TS-610 (Cabot), 12g of silane coupling agent KH-550 (Longcheng Organosilicon), 15g of curing agent TPA-B80X (Dornex), 15g of defoamer TEGO-810 (Degao), 25g of leveling agent TEGO-2300 (Degao), 10g of acid catalyst TECH-8500N (Tiger Reagent), and 1.2g of antioxidant AT-168 (Albemarle) to (1) in sequence and stir at room temperature for 30min.

[0068] (3) Stop stirring and grind the mixture in (2) thoroughly with a three-roll mill.

[0069] (4) Filter the mixture in (3) and finally seal it in a jar.

[0070] Comparative Example 1 (1) Add 400g of thermoplastic polyurethane resin IROSTIC S 8743 (Huntsman), 120g of terpene resin (Arakawa Chemical), 80g of petroleum resin (Eastman), and 900g of diethylene glycol butyl ether acetate (Sinopharm) to the reactor and stir at 500rpm and 60℃ for 8h.

[0071] (2) After cooling, add 20g of filler TS-720 (Cabot), 15g of silane coupling agent KH-560 (Longcheng Organosilicon), 10g of curing agent TKA-B75S (Dornex), 15g of defoamer BYK-066N (BYK), 30g of leveling agent BYK-320 (BYK), 15g of acid catalyst NACURE-2500 (King's Chemical), and 1g of antioxidant Ingonox1010 (BASF) to (1) and stir at room temperature for 30min.

[0072] (3) Stop stirring and grind the mixture in (2) thoroughly with a three-roll mill.

[0073] (4) Filter the mixture in (3) and finally seal it in a jar.

[0074] Comparative Example 2 (1) 400g thermoplastic polyester resin ES-660 (SK Chemicals), 120g terpene resin (Arakawa Chemicals), 80g petroleum resin (Eastman Chemicals), and 900g diethylene glycol butyl ether acetate (Sinopharm) were added to the reactor and stirred at 500rpm and 60℃ for 8h.

[0075] (2) After cooling, add 20g of filler TS-720 (Cabot), 15g of silane coupling agent KH-560 (Longcheng Organosilicon), 10g of curing agent TKA-B75S (Dornex), 15g of defoamer BYK-066N (BYK), 30g of leveling agent BYK-320 (BYK), 15g of acid catalyst NACURE-2500 (King's Chemical), and 1g of antioxidant Ingonox1010 (BASF) to (1) and stir at room temperature for 30min.

[0076] (3) Stop stirring and grind the mixture in (2) thoroughly with a three-roll mill.

[0077] (4) Filter the mixture in (3) and finally seal it in a jar.

[0078] Comparative Example 3 (1) Add 300g of thermoplastic polyurethane resin IROSTIC S 8743 (Huntsmay), 100g of thermoplastic polyester resin ES-660 (SK Chemicals), and 900g of diethylene glycol butyl ether acetate (Sinopharm) to the reactor and stir at 500rpm and 60℃ for 8h.

[0079] (2) After cooling, add 20g of filler TS-720 (Cabot), 15g of silane coupling agent KH-560 (Longcheng Organosilicon), 10g of curing agent TKA-B75S (Dornex), 15g of defoamer BYK-066N (BYK), 30g of leveling agent BYK-320 (BYK), 20g of acid catalyst NACURE-2500 (King's Chemical), and 1g of antioxidant Ingonox1010 (BASF) to (1) and stir at room temperature for 30min.

[0080] (3) Stop stirring and grind the mixture in (2) thoroughly with a three-roll mill.

[0081] (4) Filter the mixture in (3) and finally seal it in a jar.

[0082] Comparative Example 4 (1) Add 300g of thermoplastic polyurethane resin IROSTIC S 8743 (Huntsman), 100g of thermoplastic polyester resin ES-660 (SK Chemicals), 120g of terpene resin (Arakawa Chemicals), 80g of petroleum resin (Eastman), and 900g of diethylene glycol butyl ether acetate (Sinopharm) to the reactor and stir at 500rpm and 60℃ for 8h.

[0083] (2) After cooling, add 20g of filler TS-720 (Cabot), 15g of silane coupling agent KH-560 (Longcheng Organosilicon), 15g of defoamer BYK-066N (BYK), 30g of leveling agent BYK-320 (BYK), 15g of acid catalyst NACURE-2500 (King's Chemical), and 1g of antioxidant Ingonox1010 (BASF) to (1) and stir at room temperature for 30min.

[0084] (3) Stop stirring and grind the mixture in (2) thoroughly with a three-roll mill.

[0085] (4) Filter the mixture in (3) and finally seal it in a jar.

[0086] Comparative Example 5 (1) Add 300g of thermoplastic polyurethane resin IROSTIC S 8743 (Huntsman), 100g of thermoplastic polyester resin ES-660 (SK Chemicals), 120g of terpene resin (Arakawa Chemicals), 80g of petroleum resin (Eastman), and 900g of diethylene glycol butyl ether acetate (Sinopharm) to the reactor and stir at 500rpm and 60℃ for 8h.

[0087] (2) After cooling, add 20g of filler TS-720 (Cabot), 15g of silane coupling agent KH-560 (Longcheng Organosilicon), 10g of curing agent TKA-B75S (Dornex), 15g of defoamer BYK-066N (BYK), 30g of leveling agent BYK-320 (BYK), and 1g of antioxidant Ingonox1010 (BASF) to (1) and stir at room temperature for 30min.

[0088] (3) Stop stirring and grind the mixture in (2) thoroughly with a three-roll mill.

[0089] (4) Filter the mixture in (3) and finally seal it in a jar.

[0090] Comparative Example 6 (1) Add 300g of thermoplastic polyurethane resin IROSTIC S 8743 (Huntsman), 100g of thermoplastic polyester resin ES-660 (SK Chemicals), 120g of hydrogenated rosin resin (Arakawa Chemicals), 80g of petroleum resin (Eastman), and 900g of diethylene glycol butyl ether acetate (Sinopharm) to the reactor and stir at 500rpm and 60℃ for 8h.

[0091] (2) After cooling, add 20g of filler TS-720 (Cabot), 15g of silane coupling agent KH-560 (Longcheng Organosilicon), 10g of curing agent TKA-B75S (Dornex), 15g of defoamer BYK-066N (BYK), 30g of leveling agent BYK-320 (BYK), 15g of acid catalyst NACURE-2500 (King's Chemical), and 1g of antioxidant Ingonox1010 (BASF) to (1) and stir at room temperature for 30min.

[0092] (3) Stop stirring and grind the mixture in (2) thoroughly with a three-roll mill.

[0093] (4) Filter the mixture in (3) and finally seal it in a jar.

[0094] Comparative Example 7 (1) Add 400g of thermoplastic polyurethane resin IROSTIC S 8743 (Huntsmay), 100g of thermoplastic polyester resin ES-660 (SK Chemicals), 120g of terpene resin (Arakawa Chemicals), 80g of liquid rosin resin (Arakawa Chemicals), and 900g of diethylene glycol butyl ether acetate (Sinopharm) to the reactor and stir at 500rpm and 60℃ for 8h.

[0095] (2) After cooling, add 20g of filler TS-720 (Cabot), 15g of silane coupling agent KH-560 (Longcheng Organosilicon), 10g of curing agent TKA-B75S (Dornex), 15g of defoamer BYK-066N (BYK), 30g of leveling agent BYK-320 (BYK), 15g of acid catalyst NACURE-2500 (King's Chemical), and 1g of antioxidant Ingonox1010 (BASF) to (1) and stir at room temperature for 30min.

[0096] (3) Stop stirring and grind the mixture in (2) thoroughly with a three-roll mill.

[0097] (4) Filter the mixture in (3) and finally seal it in a jar.

[0098] The waterproof adhesives prepared in the above embodiments and comparative examples were tested, and the specific test methods and results are as follows: Curing conditions: 100℃ for 5 minutes Secondary processing bonding conditions: 130℃, 5kg flat pressing for 30min Printing screen: 80 mesh Printed dry film thickness: 40μm Peel strength: A 10cm*1cm*40μm adhesive strip was printed on an aluminum substrate, then cured and dried. Immediately afterwards, a layer of PET was attached to the adhesive film, and flat-pressed at 130℃ with 5kg for 30min. After cooling to room temperature, the narrow PET side of the adhesive film was torn 180° using a tensile testing machine, and the peel force was recorded as n N. The peel strength is then n N / cm (PET / metal).

[0099] A schematic diagram of the peel strength test is shown below. Figure 1 As shown.

[0100] Weather resistance test: The prepared sample was placed in a 70℃, 90%RH environmental test chamber for 168 hours to test the peel strength.

[0101] Thermal cycling: The prepared sample is placed in a temperature-controlled chamber and cycled at -40℃ for 2 hours and then at -60℃ for 2 hours for 1 hour. A total of 50 cycles are performed to test the peel strength.

[0102] Waterproof test: A closed ring pattern with an inner width of 1mm and a thickness of 40μm is printed on an aluminum substrate printed with conductive paste. After curing and drying, a layer of PET is attached to the film and flat-pressed at 130℃ and 5kg for 30min. After cooling to room temperature, it is placed in a 25℃ constant temperature water bath. If the resistance change exceeds 30%, it is considered a failure.

[0103] Liquid resistance test: A closed annular pattern with an inner width of 1 mm and a thickness of 40 μm is printed on an aluminum substrate printed with conductive paste. After curing and drying, a layer of PET is attached to the film and then flat-pressed at 130℃ and 5 kg for 30 min. After cooling to room temperature, it is placed in cola, coffee, and ethanol at a constant temperature of 25℃. If the resistance change exceeds 30%, it is considered a failure.

[0104] Acid and alkali resistance test: Prepare a dilute hydrochloric acid solution with pH=2 and a sodium hydroxide solution with pH=13. Place the prepared ring pattern sample into the constant temperature acid and alkali solution at 25℃. If the resistance change exceeds 30%, it is considered as failure.

[0105] The test results for each embodiment and comparative example are shown in Table 1 and Table 2.

[0106] Table 1

[0107] Table 2

[0108] Furthermore, the curing conditions and printability-related properties of the composition of the present invention were investigated. The specific properties are shown in Table 3. As can be seen from Table 3, it has good printability, and 30 min is its optimal curing time.

[0109] Table 3

[0110] The above description is merely an embodiment of this application and is not intended to limit the scope of protection of this application. Any modifications, equivalent substitutions, and improvements made within the spirit and scope of this application are included within the scope of protection of this application.

Claims

1. A waterproof adhesive composition comprising: Thermoplastic polyurethane resins, thermoplastic polyester resins, curing agents, terpene resins, and petroleum resins.

2. The waterproof adhesive composition according to claim 1, characterized in that, The waterproof adhesive composition satisfies at least one of the following conditions: The thermoplastic polyurethane resin accounts for 10%-20% of the total mass of the waterproof adhesive composition; The thermoplastic polyester resin accounts for 5%-10% of the total mass of the waterproof adhesive composition; The curing agent accounts for 0.5%-1% of the total mass of the waterproof adhesive composition; The terpene resin accounts for 5%-9% of the total mass of the waterproof adhesive composition; or The petroleum resin accounts for 4%-7.5% of the total mass of the waterproof adhesive composition.

3. As described in claim 1 or 2, characterized in that, The waterproof adhesive composition includes: The waterproof adhesive composition comprises 10%-20% by weight of the thermoplastic polyurethane resin; 5%-10% by weight of the thermoplastic polyester resin; 0.5%-1% by weight of the curing agent; 5%-9% by weight of the terpene resin; and 4%-7.5% by weight of the petroleum resin.

4. The waterproof adhesive composition according to any one of claims 1 to 3, characterized in that, The waterproof adhesive composition satisfies at least one of the following conditions: The thermoplastic polyurethane may be selected from one or more of the following: IROSTIC S 6148, IROSTIC S8743, IROSTIC S 7614, IROSTIC S 9815, Lubrizol 5703, or Lubrizol 5715; The thermoplastic polyester may be selected from one or more of the following: ES-420, ES-660, ES-680, ES-901, GK-103, GK-270, or GK-240; or The curing agent includes a latent isocyanate curing agent.

5. The waterproof adhesive composition according to any one of claims 1 to 4, characterized in that, The waterproof adhesive composition further includes one or more of the following: diluent, coupling agent, defoamer, leveling agent, filler, acid catalyst, or antioxidant.

6. The waterproof adhesive composition according to claim 5, characterized in that, The waterproof adhesive composition satisfies at least one of the following conditions: The diluent accounts for 50%-60% of the total mass of the waterproof adhesive composition; the coupling agent accounts for 0.5%-1% of the total mass of the waterproof adhesive composition; the defoamer accounts for 0.5%-1% of the total mass of the waterproof adhesive composition; the leveling agent accounts for 0.5%-1% of the total mass of the waterproof adhesive composition; the filler accounts for 1%-2% of the total mass of the waterproof adhesive composition; the acid catalyst accounts for 0.5%-1% of the total mass of the waterproof adhesive composition; or the antioxidant accounts for 0.05%-0.08% of the total mass of the waterproof adhesive composition.

7. The waterproof adhesive composition according to claim 5 or 6, characterized in that, The waterproof adhesive composition satisfies at least one of the following conditions: The diluent may be selected from one or more of the following: diethylene glycol phenyl ether acetate, diethylene glycol butyl ether acetate, a mixture of dicarboxylic acid esters, hexadecyl alcohol ester, butyl acetate, diethylene glycol benzoate, propylene glycol monomethyl ether, or N-methylpyrrolidone; the coupling agent includes silane coupling agents; the defoamer includes silicone defoamers; the leveling agent includes silicone leveling agents; the filler includes hydrophobic fumed silica; the acid catalyst includes sulfonate acid catalysts; or the antioxidant includes phenolic antioxidants.

8. The application of the waterproof adhesive composition according to any one of claims 1-7 in the preparation of waterproof adhesives.

9. A method for preparing a waterproof adhesive, comprising the following steps: Thermoplastic polyurethane resin, thermoplastic polyester resin, terpene resin and petroleum resin are mixed at 60℃~80℃ and 100~150rpm for the first stirring until completely dissolved. Add the remaining components and stir a second time at 20℃~25℃ and 80~150rpm until completely dissolved to obtain the waterproof adhesive precursor; and The waterproof adhesive precursor is ground, dispersed, and filtered to obtain the waterproof adhesive.

10. The method for preparing the waterproof adhesive according to claim 9, characterized in that, The method includes at least one of the following steps: Thermoplastic polyurethane resin, thermoplastic polyester resin, terpene resin, and petroleum resin were mixed at 60°C and 150 rpm and stirred for the first time until completely dissolved. Add the remaining components and stir a second time at 20°C and 80-120 rpm until completely dissolved to obtain the waterproof adhesive precursor; or The grinding parameters are 40μm / 20μm; rotation speed 200-400rpm; roller temperature 20-25℃.

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