Backing adhesive emulsion having high bonding strength, and starting material composition thereof, preparation method therefor and use thereof

Abstract

Disclosed in the present invention are a backing adhesive emulsion having high bonding strength, and a starting material composition thereof, a preparation method therefor and a use thereof. The starting material composition comprises the following components in parts by weight: 6-10 parts of a hard monomer, 31-35 parts of a soft monomer, 1.8-2.2 parts of a protective monomer, 0.08-0.12 parts of an organosilicon monomer, 2.3-2.7 parts of an emulsifier, and 0.18-0.22 parts of an initiator; the protective monomer comprises acrylamide and acrylic acid in a mass ratio of (0.6-1):1. The backing adhesive emulsion of the present invention has good bonding strength and emulsion stability, and all starting materials used are conventional starting materials and are used in conventional amounts, resulting in low cost.

Description

A high-adhesion-strength adhesive emulsion, its raw material composition, preparation method, and application.

[0001] This application claims priority to Chinese patent application 2025100854664, filed on January 20, 2025. The entire contents of the aforementioned Chinese patent application are incorporated herein by reference. Technical Field

[0002] This invention belongs to the field of coating technology, specifically relating to a high-adhesion-strength adhesive emulsion, its raw material composition, preparation method, and application. Background Technology

[0003] Adhesive emulsions are water-based adhesives primarily composed of polyacrylic resin, additives, and water. They possess excellent adhesion, high bonding strength, environmental friendliness, and ease of processing. Adhesive emulsions are widely used in stationery manufacturing, automotive interior manufacturing, packaging, furniture manufacturing, tile bonding, and many other fields, providing convenient and practical bonding solutions for various industries. However, existing water-based acrylic adhesive emulsions cannot simultaneously achieve both strong adhesion and emulsion stability. Traditional water-based acrylic emulsions exhibit poor stability during substrate coating, leading to demulsification and gelation, which affects subsequent bonding strength and reduces the effectiveness of the adhesive coating.

[0004] To address this issue, the art typically involves modifying the latex particles or their structure within the emulsion to improve their coating stability and adhesion strength on the substrate. For example, the properties of the latex particles can be improved by altering the ratio of hard to soft segments, or by modifying the preparation system by introducing functional monomers.

[0005] Conventional methods for improving the stability of latex particles may increase the cost of emulsion manufacturing and sacrifice the adhesive strength and degree of polymerization of the latex particles. Therefore, how to ensure the stability of latex particles in the emulsion to achieve good coating results without affecting its adhesive strength is a technical challenge that urgently needs to be solved in this field. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a high-adhesion-strength adhesive emulsion, its raw material composition, preparation method, and application. The adhesive emulsion provided by this invention exhibits good adhesive strength and emulsion stability, uses conventional raw materials and dosages, and has a low cost.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] In one aspect, the present invention provides a raw material composition for a high-adhesion-strength adhesive emulsion, comprising the following components in parts by weight:

[0009] 6–10 parts hard monomer, 31–35 parts soft monomer, 1.8–2.2 parts protective monomer, 0.08–0.12 parts organosilicon monomer, 2.3–2.7 parts emulsifier, and 0.18–0.22 parts initiator;

[0010] The protective monomer comprises acrylamide and acrylic acid in a mass ratio of (0.6 to 1):1.

[0011] In some embodiments, the mass ratio of the hard monomer to the soft monomer is 1:(3.1 to 5.9);

[0012] In some embodiments, the hard monomer includes methyl methacrylate and styrene monomers;

[0013] In some embodiments, the soft monomer comprises n-butyl acrylate and isooctyl acrylate in a mass ratio of 1:(0.82-0.85);

[0014] In some embodiments, the organosilicon monomer is a silane monomer containing vinyl groups;

[0015] In some embodiments, the emulsifier is selected from at least one of ethoxylated fatty alcohol xanthyl succinate disodium salt, alkyl sulfosuccinate sodium salt, and lauryl polyoxyethylene ether sulfosuccinate disodium salt.

[0016] In some embodiments, the methyl methacrylate is present in parts by weight of 1 to 3 parts;

[0017] In some embodiments, the styrene monomer is selected from at least one of 3-chlorostyrene, styrene, and p-chlorostyrene;

[0018] In some embodiments, the organosilicon monomer is selected from one of vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriacetoxysilane;

[0019] In some embodiments, the raw material composition of the high-adhesion-strength adhesive emulsion further includes 52 to 56 parts of water.

[0020] In another aspect, the present invention provides a method for preparing a high-adhesion-strength adhesive emulsion, comprising at least:

[0021] (1) The soft monomer, hard monomer, protective monomer, part water, part emulsifier and part initiator are mixed and pre-emulsified to obtain the emulsified monomer;

[0022] (2) Add the remaining emulsifier and water to the reaction flask and heat to 82-86°C. Add the remaining initiator to carry out the pyrolysis reaction. Then add 2.5-3.1% of the emulsified monomer and organosilicon monomer to the reaction flask and carry out the initial reaction.

[0023] (3) After the above reaction is completed, add the remaining emulsified monomer dropwise over 3.5 to 4 hours, and then continue the reaction at a constant temperature.

[0024] (4) Add the oxidant and reducing agent to the reaction flask, pass through the oxidation-reduction system, keep the temperature for reaction, cool down to below 45°C, add pH adjuster to adjust the pH value of the system to 7-9, and it is ready.

[0025] In step (1), the amount of water used is 30-35% of the total weight of water;

[0026] In step (1), the amount of the emulsifier used is 66-74% of the total weight of the emulsifier;

[0027] In step (1), the amount of the initiator is 48-52% of the total weight of the initiator;

[0028] In step (2), the pyrolysis reaction takes 3 to 4 minutes;

[0029] In step (2), the initial reaction time is 5 to 6 minutes;

[0030] In step (3), the temperature of the dripping is 82-86°C;

[0031] In step (3), the heat preservation reaction time is 1 to 1.5 hours;

[0032] In step (3), the temperature of the heat preservation reaction is 84-87℃;

[0033] In step (4), the heat preservation reaction time is 0.5 to 1 hour;

[0034] In step (4), the temperature of the heat preservation reaction is 72-76℃;

[0035] In step (4), the cooling temperature is 30-40°C.

[0036] The mass ratio of the partial emulsifier in step (1) to the remaining emulsifier in step (2) is 1:(0.2 to 0.6).

[0037] In a third aspect, the present invention also provides a high-adhesion-strength adhesive emulsion, which is prepared by the above-described method for preparing a high-adhesion-strength adhesive emulsion.

[0038] In a fourth aspect, the present invention also provides an application of the above-mentioned high-adhesion-strength adhesive emulsion in the field of wall decoration.

[0039] The reagents and raw materials used in this invention are all commercially available.

[0040] The positive and progressive effects of this invention are as follows:

[0041] (1) The present invention adopts a seed polymerization process. The resulting adhesive emulsion uses pre-emulsified monomers as the seed emulsion structure. By using acrylate monomers in the optimal ratio, the particle size distribution and molecular weight of the later polymerization are effectively controlled. The remaining emulsified monomers are grafted and distributed at the end of the seed emulsion shell chain.

[0042] (2) In addition to the seed synthesis design, the present invention also adds vinyl silane monomers (organosilicon monomers) to the seed synthesis end. Vinyl silane monomers can undergo coupling reactions with polar groups such as hydroxyl and carboxyl groups in acrylic acid molecules to form strong covalent bonds, thereby improving the later film strength of the adhesive emulsion coating.

[0043] (3) In the process of preparing high-adhesion-strength adhesive emulsion, the inventors discovered that the order of addition of organosilicon monomers has a significant impact on the product performance of the high-adhesion-strength adhesive emulsion. First, the seed monomer in the reaction flask system undergoes polymerization with the organosilicon monomer. A small portion of the pre-emulsified monomer undergoes preliminary seed emulsion polymerization in the emulsifier under the action of an initiator. After forming a sufficient number of silicone latex particles with sufficiently small particle size in the micelles, it continues to polymerize with other large remaining monomer raw materials. The molecular weight of the polymer continuously increases, and the corresponding polymer particles also gradually grow, forming a silicon core-shell polymer dispersion. This order of addition ensures that the organosilicon monomer fully undergoes coupling reaction with the polar groups such as hydroxyl and carboxyl groups in the acrylic acid molecule, and that the vinyl functional groups can be uniformly grafted onto the long chain shell of the polymer. The reaction is stable, the particle size is moderate, and the strength after crosslinking can be improved.

[0044] (4) The preparation method of the high adhesive strength backing emulsion provided by the present invention is easy to implement, the polymerization reaction rate is stable, the apparent particle size of the latex particles is moderate, and the amount of slag is low. Through this process, the coating properties and adhesive strength of the backing emulsion can be significantly enhanced.

[0045] (5) The adhesive emulsion provided by the present invention has excellent stability and can effectively coat the substrate. It also has high adhesive performance. The adhesive strength after immersion in water, heat aging and freeze-thaw cycle exceeds the standard by more than 200%, and the actual use effect is excellent. Detailed Implementation

[0046] The present invention will now be described in detail with reference to embodiments, providing a clear and complete description of the technical solutions to facilitate understanding of the invention by those skilled in the art. The described embodiments are merely some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention. Furthermore, all raw materials mentioned below, unless otherwise specified, are commercially available products; and all process steps or preparation methods not mentioned in detail are process steps or preparation methods known to those skilled in the art.

[0047] Example 1

[0048] A high-adhesion-strength adhesive emulsion, the raw material composition of which includes the following components in parts by weight, as shown in Table 1;

[0049] Table 1. Weight parts of each component in the raw materials

[0050] Here, the emulsification bottle system refers to the material components added to the emulsification bottle, and the reaction bottle system refers to the material components added to the reaction bottle.

[0051] The preparation method includes the following steps:

[0052] (1) 1.7 parts of sodium alkyl sulfosuccinate monoester, 18 parts of water, 5 parts of styrene, 1 part of methyl methacrylate, 19 parts of n-butyl acrylate, 16 parts of isooctyl acrylate, 1 part of acrylic acid, 0.8 parts of acrylamide, and 0.09 parts of sodium persulfate were stirred and emulsified to obtain an emulsified monomer.

[0053] (2) Add the remaining emulsifier and water to the reaction flask and heat it to 82-86°C. Then add the remaining initiator. After the pyrolysis reaction for 3 minutes, take 2.8% of the emulsified monomer and the organosilicon monomer and add them to the reaction flask. Then react for another 5 minutes.

[0054] (3) After the above reaction is completed, the remaining emulsifying monomer is added dropwise over a period of 225 minutes;

[0055] (4) After the emulsifying monomers are added, keep warm at 84-87℃ for 1.2 hours;

[0056] (5) Add the oxidant and reducing agent to the reaction flask, and after passing through the redox system, keep the reaction at 72-76℃ for 0.5h, then cool down to 40℃, add pH adjuster to adjust the pH value of the system to 7-9, and it is ready.

[0057] Example 2

[0058] A high-adhesion-strength adhesive emulsion, the raw material composition of which includes the following components in parts by weight, as shown in Table 2;

[0059] Table 2. Weight parts of each component in the raw materials

[0060] The emulsification bottle system refers to the material components added to the emulsification bottle, and the reaction bottle system refers to the material components added to the reaction bottle.

[0061] The preparation method includes the following steps:

[0062] (1) 1.8 parts of sodium alkyl sulfosuccinate monoester, 18 parts of water, 6 parts of styrene, 2 parts of methyl methacrylate, 18 parts of n-butyl acrylate, 15 parts of isooctyl acrylate, 1.1 parts of acrylic acid, 0.9 parts of acrylamide, and 0.1 parts of sodium persulfate were stirred and emulsified to obtain an emulsified monomer.

[0063] (2) Add the remaining emulsifier and water to the reaction flask and heat it to 82-86°C. Then add the remaining initiator and let it decompose for 4 minutes. Then add 2.8% of the emulsified monomer and the organosilicon monomer to the reaction flask and let it react for another 5.5 minutes.

[0064] (3) After the above reaction is completed, the remaining emulsifying monomer is added dropwise over a period of 240 minutes;

[0065] (4) After the emulsified monomers are added, keep warm at 84-87℃ for 1.5 hours;

[0066] (5) Add the oxidant and reducing agent to the reaction flask, and after passing through the redox system, keep the reaction at 72-76℃ for 0.7h, then cool down to 35℃, add pH adjuster to adjust the pH value of the system to 7-9, and it is ready.

[0067] Example 3

[0068] A high-adhesion-strength adhesive emulsion, the raw material composition of which includes the following components in parts by weight, as shown in Table 3;

[0069] Table 3. Weight parts of each component in the raw materials

[0070] The emulsification bottle system refers to the material components added to the emulsification bottle, and the reaction bottle system refers to the material components added to the reaction bottle.

[0071] The preparation method includes the following steps:

[0072] (1) 1.8 parts of sodium alkyl sulfosuccinate monoester, 18 parts of water, 7 parts of styrene, 3 parts of methyl methacrylate, 17 parts of n-butyl acrylate, 14 parts of isooctyl acrylate, 1.2 parts of acrylic acid, 1.0 parts of acrylamide, and 0.11 parts of sodium persulfate were stirred and emulsified to obtain an emulsified monomer.

[0073] (2) Add the remaining emulsifier and water to the reaction flask and heat to 82-86℃. Then add the remaining initiator. After the pyrolysis reaction for 3.5 min, take 2.8% of the emulsified monomer and the organosilicon monomer and add them to the reaction flask. Then react for another 6 min.

[0074] (3) After the above reaction is completed, the remaining emulsifying monomer is added dropwise over a period of 210 minutes;

[0075] (4) After the emulsified monomer is added, keep warm at 84-87℃ for 1 hour;

[0076] (5) Add the oxidant and reducing agent to the reaction flask material, and after passing through the oxidation-reduction system, keep the temperature at 72-76℃ for 1 hour, then cool down to 30℃, add pH adjuster to adjust the pH value of the system to 7-9, and it is ready.

[0077] The present invention also provides the following comparative examples.

[0078] Comparative Example 1

[0079] The only difference from Example 3 is that the amount of n-butyl acrylate is 16 parts and the amount of isooctyl acrylate is 15 parts.

[0080] Comparative Example 2

[0081] The only difference from Example 3 is that the timing of the addition of vinyltrimethoxysilane is different; it is added in step (1).

[0082] Comparative Example 3

[0083] The only difference from Example 3 is that the amount of n-butyl acrylate used is 31 parts, and isooctyl acrylate is not added.

[0084] Comparative Example 4

[0085] The only difference from Example 3 is that the amount of styrene used is 10 parts, and methyl methacrylate is not added.

[0086] Comparative Example 5

[0087] The only difference from Example 1 is that the amount of methyl methacrylate is 5 parts, the amount of styrene is 1 part, the amount of acrylic acid is 0.8 parts, and the amount of acrylamide is 1 part.

[0088] Comparative Example 6

[0089] The product purchased from the market is YS-8569, manufactured by Guangdong Yinyang Environmental Protection New Materials Co., Ltd.

[0090] Product performance testing

[0091] The emulsions from the examples and comparative examples were tested according to the following standards and methods:

[0092] I. Emulsion stability: Tested according to GB / T 20623-2006 Test method for emulsions used in latex paints.

[0093] II. Bond strength test: The test shall be conducted in accordance with T / CBMF 87-2020.

[0094] The performance of the products of Examples 1-3 and Comparative Examples 1-6 of this application was tested, and the results are shown in Table 4.

[0095] Table 4

[0096] As can be seen from the table above, the comprehensive strength values ​​of Examples 1 to 3 are all excellent, and their comprehensive performance meets the evaluation requirements of GB / T 20623-2006 and T / CBMF 87-2020 standards. In the above-mentioned evaluation items of Comparative Examples 1 to 5 and commercially available products, Comparative Examples 2 and 4 and 5 all failed to meet the standard requirements. Comparative Examples 1, 3 and 6 (commercially available products) can meet two standards, but their bonding strength is lower than that of the Examples.

[0097] Finally, it should be noted that in this invention, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus.

[0098] Although this disclosure has been described above through specific embodiments, it should be understood that those skilled in the art can devise various modifications, improvements, or equivalents to this disclosure within the spirit and scope of the appended solutions. Such modifications, improvements, or equivalents should also be considered to be included within the scope of protection claimed in this disclosure.

Claims

1. A raw material composition for a high-adhesion-strength adhesive emulsion, characterized in that, It comprises the following components in parts by weight: 6–10 parts hard monomer, 31–35 parts soft monomer, 1.8–2.2 parts protective monomer, 0.08–0.12 parts organosilicon monomer, 2.3–2.7 parts emulsifier, and 0.18–0.22 parts initiator; The protective monomer comprises acrylamide and acrylic acid in a mass ratio of (0.6 to 1):

1.

2. The raw material composition of the high-adhesion-strength adhesive emulsion according to claim 1, characterized in that, The mass ratio of the hard monomer to the soft monomer is 1:(3.1~5.9); And / or, the hard monomers include methyl methacrylate and styrene monomers; And / or, the soft monomer comprises n-butyl acrylate and isooctyl acrylate in a mass ratio of 1:(0.82-0.85); And / or, the organosilicon monomer is a silane monomer containing vinyl groups; And / or, the emulsifier is selected from at least one of ethoxylated fatty alcohol xanthyl succinate disodium salt, alkyl sulfosuccinate sodium salt, and lauryl polyoxyethylene ether sulfosuccinate disodium salt.

3. The raw material composition of the high-adhesion-strength adhesive emulsion according to claim 1, characterized in that, The methyl methacrylate is present in 1 to 3 parts by weight; And / or, the styrene monomer is selected from at least one of 3-chlorostyrene, styrene, and p-chlorostyrene; And / or, the organosilicon monomer is selected from one of vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriacetoxysilane.

4. The raw material composition of the high-adhesion-strength adhesive emulsion according to claim 1, characterized in that, The raw material composition of the high-adhesion-strength adhesive emulsion further includes 52 to 56 parts of water.

5. A method for preparing a high-adhesion-strength adhesive emulsion, characterized in that, The raw materials for the high-adhesion-strength adhesive emulsion include the raw material composition for the high-adhesion-strength adhesive emulsion as described in any one of claims 1 to 4, and the method includes the following steps: (1) The soft monomer, hard monomer, protective monomer, part water, part emulsifier and part initiator are mixed and pre-emulsified to obtain the emulsified monomer; (2) Add the remaining emulsifier and water to the reaction flask and heat to 82-86°C. Add the remaining initiator to carry out the pyrolysis reaction. Then add 2.5-3.1% of the emulsified monomer and organosilicon monomer to the reaction flask and carry out the initial reaction. (3) After the above reaction is completed, add the remaining emulsified monomer dropwise over 3.5 to 4 hours, and then continue the reaction at a constant temperature. (4) Add the oxidant and reducing agent to the reaction flask, pass through the oxidation-reduction system, keep the temperature for reaction, cool down to below 45°C, add pH adjuster to adjust the pH value of the system to 7-9, and it is ready.

6. The method for preparing the high-adhesion-strength adhesive emulsion according to claim 5, characterized in that, The preparation method satisfies at least one of the following conditions: In step (1), the amount of water used is 30-35% of the total weight of water; In step (1), the amount of the emulsifier used is 66-74% of the total weight of the emulsifier; In step (1), the amount of the initiator is 48-52% of the total weight of the initiator; In step (2), the pyrolysis reaction takes 3 to 4 minutes; In step (2), the initial reaction time is 5 to 6 minutes; In step (3), the temperature of the dripping is 82-86°C; In step (3), the heat preservation reaction time is 1 to 1.5 hours; In step (3), the temperature of the heat preservation reaction is 84-87℃; In step (4), the heat preservation reaction time is 0.5 to 1 hour; In step (4), the temperature of the heat preservation reaction is 72-76℃; In step (4), the cooling temperature is 30-40°C.

7. The method for preparing the high-adhesion-strength adhesive emulsion according to claim 3, characterized in that, The mass ratio of the partial emulsifier in step (1) to the remaining emulsifier in step (2) is 1:(0.2 to 0.6).

8. A high-adhesion-strength adhesive emulsion, characterized in that, It is prepared by the method for preparing high-adhesion-strength adhesive emulsion as described in any one of claims 5 to 7.

9. The application of the high-adhesion-strength adhesive emulsion according to claim 8 in the field of wall decoration.

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