High-weather-resistance pressure-sensitive adhesive and preparation method thereof

Abstract

The invention belongs to the technical field of pressure-sensitive adhesives, and discloses a high-weather-resistance pressure-sensitive adhesive and a preparation method thereof. The pressure-sensitive adhesive is prepared from the following raw materials in parts by weight: 30 to 40 parts of a soft monomer, 5 to 10 parts of a hard monomer, 1 to 3 parts of a functional monomer, 50 to 80 parts of a solvent, 1 to 5 parts of alkylene polyhedral oligomeric silsesquioxane, 1 to 3 parts of pentalyn, 0.5 to 1 part of an initiator and 0.5 to 0.8 part of a curing agent. The hard monomer is a mixture of methyl methacrylate and isobornyl acrylate, and the mass ratio of methyl methacrylate to isobornyl acrylate is (3-5): 1. The components interact with one another, the product structure is stable, the viscosity and peel strength of the pressure-sensitive adhesive are greatly improved, and the pressure-sensitive adhesive has good weather resistance, can be applied to high-temperature and high-humidity scenes for a long time, cannot be aged and decomposed due to simple weather changes and harsh working environments, is good in uniformity and stability, and can be widely applied to high-temperature and high-humidity scenes. The method is suitable for large-scale application.

Description

Technical Field

[0001] The invention belongs to the technical field of pressure-sensitive adhesives, and more specifically relates to a high-weather-resistant pressure-sensitive adhesive and a preparation method thereof. Background Art

[0002] Pressure-sensitive adhesive is a kind of adhesive that is sensitive to pressure, does not require heating, solvents, or high pressure, and can be bonded with just a little pressure or a press of the finger. Its characteristics are that it is easy to stick, easy to peel, and can be peeled without damage. Because of the unique properties of pressure-sensitive adhesive, with the continuous expansion of its application fields, pressure-sensitive adhesive has been industrialized in many fields with its excellent performance. For example, in the manufacturing process of large containers, due to the large area of ​​the panel and easy bending, it is necessary to use reinforcing ribs to fix it. The contact area between the reinforcing rib and the panel is small, but as a load-bearing part, it needs to be subjected to force, so a high-strength structural adhesive is required for bonding, so pressure-sensitive adhesive has become the first choice in industrial applications.

[0003] Among them, acrylic pressure-sensitive adhesives have been widely used, ranging from aerospace, automobiles, ships, railways and construction to electronic products, household instruments, toys and handicrafts. Since some electronic products need to be exposed to high temperature and high humidity environments and strong sunlight, pressure-sensitive adhesives need to have a certain degree of weather resistance; at the same time, electronic devices will release heat more or less during use; in addition, most electronic device manufacturing processes include welding methods, which requires tape products to have good high temperature tolerance. However, acrylic pressure-sensitive adhesives are easily affected by the external environment, resulting in a decrease in bonding strength and poor weather resistance. In actual applications, it is difficult to meet the needs under different natural conditions.

[0004] Therefore, how to provide a highly weather-resistant pressure-sensitive adhesive and a preparation method thereof is a problem that those skilled in the art need to solve urgently. Summary of the invention

[0005] In order to overcome the shortcomings and deficiencies in the prior art, the present invention provides a highly weather-resistant pressure-sensitive adhesive and a preparation method thereof.

[0006] In order to achieve the above object, the present invention adopts the following technical solution:

[0007] A high weather-resistant pressure-sensitive adhesive comprises the following raw materials, measured by weight: 30-40 parts of soft monomers, 5-10 parts of hard monomers, 1-3 parts of functional monomers, 50-80 parts of solvents, 1-5 parts of olefin-based cage-type silsesquioxanes, 1-3 parts of rosin pentaerythritol esters, 0.5-1 parts of initiators, and 0.5-0.8 parts of curing agents.

[0008] Preferably, the soft monomer is selected from one or more of butyl acrylate, isooctyl methacrylate, ethyl acrylate, lauryl acrylate and butyl methacrylate.

[0009] Preferably, the hard monomer is a mixture of methyl methacrylate and isobornyl acrylate.

[0010] Preferably, the mass ratio of methyl methacrylate to isobornyl acrylate is 3-5:1.

[0011] Preferably, the functional monomer is selected from one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxyethyl methacrylate.

[0012] Preferably, the olefin-based cage silsesquioxane is selected from one or more of vinyl-cage silsesquioxane and methacryl-cage silsesquioxane.

[0013] Preferably, the solvent is selected from one or more of toluene, ethyl acetate and butanone.

[0014] Preferably, the initiator is selected from one or more of dibenzoyl peroxide, dilauroyl peroxide, dicumyl peroxide, azobisisobutyronitrile and azobisisoheptylnitrile.

[0015] Preferably, the curing agent is selected from one or more of triethylenediamine, zinc isooctanoate, and aluminum triacetylacetonate.

[0016] The present invention also provides a method for preparing the above-mentioned high weather-resistant pressure-sensitive adhesive, comprising the following steps:

[0017] (1) Add soft monomer, hard monomer, functional monomer and solvent into a reaction vessel, introduce nitrogen to expel air, add initiator, raise the temperature to 70-80°C, and react for 4-6 hours;

[0018] (2) Continue to add olefin-based cage-type silsesquioxane and rosin pentaerythritol ester, react for 2-3 hours, cool to room temperature, add curing agent, stir for 0.5-1 hour, and obtain a pressure-sensitive adhesive.

[0019] It can be seen from the above technical solution that, compared with the prior art, the present invention provides a highly weather-resistant pressure-sensitive adhesive and a preparation method thereof, which has the following beneficial effects:

[0020] (1) The components of the present invention interact with each other, and the product structure is stable, which greatly improves the viscosity and peel strength of the pressure-sensitive adhesive and has good weather resistance. The pressure-sensitive adhesive can be used in high temperature and high humidity scenes for a long time, and will not age or decompose due to simple weather changes and harsh working environments. It has good uniformity and stability and is suitable for large-scale applications.

[0021] (2) The present invention adds a certain amount of olefin-based cage-type silsesquioxane to enrich the spatial structure of the polymer, improve the high temperature resistance of the pressure-sensitive adhesive, and maintain excellent bonding strength even in a high temperature and high humidity environment. The present invention also uses methyl methacrylate and isobornyl acrylate as hard monomers, which have a high glass transition temperature. Under a suitable ratio, the pressure-sensitive adhesive can have excellent high temperature resistance and avoid the problem of adhesion failure when used in a high temperature environment. Rosin pentaerythritol ester can enhance the adhesion and stickiness of the pressure-sensitive adhesive, so that the pressure-sensitive adhesive can better adhere to various substrates during application to prevent falling off, and can also prevent the pressure-sensitive adhesive from deteriorating due to oxidation during storage and use, thereby extending the service life of the pressure-sensitive adhesive. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] Example 1

[0024] A high weather-resistant pressure-sensitive adhesive comprises the following raw materials, measured by weight: 35 parts of butyl acrylate, 6 parts of methyl methacrylate, 1.5 parts of isobornyl acrylate, 2 parts of acrylic acid, 70 parts of ethyl acetate, 3 parts of octavinyl cage silsesquioxane, 2 parts of rosin pentaerythritol ester, 0.8 parts of dibenzoyl peroxide and 0.6 parts of triethylenediamine.

[0025] The preparation method of the pressure-sensitive adhesive comprises the following steps:

[0026] (1) Butyl acrylate, methyl methacrylate, isobornyl acrylate, acrylic acid, and ethyl acetate were added to a reaction vessel, nitrogen was introduced to expel the air, dibenzoyl peroxide was added, the temperature was raised to 80° C., and the reaction was carried out for 6 hours;

[0027] (2) Continue to add octavinyl cage silsesquioxane and rosin pentaerythritol ester, react for 3 hours, cool to room temperature, add triethylenediamine, stir for 1 hour, and obtain a highly weather-resistant pressure-sensitive adhesive.

[0028] Example 2

[0029] A high weather-resistant pressure-sensitive adhesive comprises the following raw materials, measured by weight: 40 parts of butyl acrylate, 8 parts of methyl methacrylate, 2 parts of isobornyl acrylate, 3 parts of acrylic acid, 80 parts of ethyl acetate, 5 parts of octavinyl cage silsesquioxane, 3 parts of rosin pentaerythritol ester, 1 part of dibenzoyl peroxide and 0.8 part of triethylenediamine.

[0030] The preparation method of the pressure-sensitive adhesive is the same as that of Example 1.

[0031] Example 3

[0032] A high weather-resistant pressure-sensitive adhesive comprises the following raw materials, measured by weight: 30 parts of butyl acrylate, 4 parts of methyl methacrylate, 1 part of isobornyl acrylate, 1 part of acrylic acid, 50 parts of ethyl acetate, 1 part of octavinyl cage silsesquioxane, 1 part of rosin pentaerythritol ester, 0.5 part of dibenzoyl peroxide and 0.5 part of triethylenediamine.

[0033] The preparation method of the pressure-sensitive adhesive is the same as that of Example 1.

[0034] Example 4

[0035] A highly weather-resistant pressure-sensitive adhesive comprises the following raw materials, measured by weight: 35 parts of isooctyl methacrylate, 6 parts of methyl methacrylate, 1.5 parts of isobornyl acrylate, 2 parts of hydroxyethyl acrylate, 70 parts of ethyl acetate, 3 parts of octavinyl cage silsesquioxane, 2 parts of rosin pentaerythritol ester, 0.8 parts of dibenzoyl peroxide and 0.6 parts of triethylenediamine.

[0036] The preparation method of the pressure-sensitive adhesive comprises the following steps:

[0037] (1) Add isooctyl methacrylate, methyl methacrylate, isobornyl acrylate, hydroxyethyl acrylate, and ethyl acetate into a reaction vessel, introduce nitrogen to expel the air, add dibenzoyl peroxide, raise the temperature to 80° C., and react for 6 hours;

[0038] (2) Continue to add octavinyl cage silsesquioxane and rosin pentaerythritol ester, react for 3 hours, cool to room temperature, add triethylenediamine, stir for 1 hour, and obtain a highly weather-resistant pressure-sensitive adhesive.

[0039] Example 5

[0040] A high weather-resistant pressure-sensitive adhesive comprises the following raw materials, measured by weight: 35 parts of lauryl acrylate, 6 parts of methyl methacrylate, 1.5 parts of isobornyl acrylate, 2 parts of hydroxyethyl methacrylate, 70 parts of toluene, 3 parts of octavinyl cage silsesquioxane, 2 parts of rosin pentaerythritol ester, 0.8 parts of azobisisobutyronitrile and 0.6 parts of zinc isooctanoate.

[0041] The preparation method of the pressure-sensitive adhesive comprises the following steps:

[0042] (1) Lauryl acrylate, methyl methacrylate, isobornyl acrylate, hydroxyethyl methacrylate, and toluene are added to a reaction vessel, nitrogen is introduced to expel the air, azobisisobutyronitrile is added, the temperature is raised to 80° C., and the reaction is carried out for 6 hours;

[0043] (2) Continue to add octavinyl cage silsesquioxane and rosin pentaerythritol ester, react for 3 hours, cool to room temperature, add zinc isooctanoate, stir for 1 hour, and obtain a highly weather-resistant pressure-sensitive adhesive.

[0044] Example 6

[0045] A high weather-resistant pressure-sensitive adhesive comprises the following raw materials, measured by weight: 20 parts of butyl acrylate, 15 parts of isooctyl methacrylate, 6 parts of methyl methacrylate, 1.5 parts of isobornyl acrylate, 1 part of hydroxyethyl acrylate, 1 part of acrylic acid, 70 parts of toluene, 3 parts of octavinyl cage silsesquioxane, 2 parts of rosin pentaerythritol ester, 0.8 parts of dilauroyl peroxide and 0.6 parts of aluminum triacetylacetonate.

[0046] The preparation method of the pressure-sensitive adhesive comprises the following steps:

[0047] (1) Butyl acrylate, isooctyl methacrylate, methyl methacrylate, isobornyl acrylate, hydroxyethyl acrylate, acrylic acid, and toluene are added to a reaction vessel, nitrogen is introduced to expel the air, dilauroyl peroxide is added, the temperature is raised to 80° C., and the reaction is carried out for 6 hours;

[0048] (2) Continue to add octavinyl cage silsesquioxane and rosin pentaerythritol ester, react for 3 hours, cool to room temperature, add aluminum triacetylacetonate, stir for 1 hour, and obtain a highly weather-resistant pressure-sensitive adhesive.

[0049] Comparative Example 1

[0050] The difference from Example 1 is that octavinyl cage silsesquioxane is not added, and the rest is the same. A pressure-sensitive adhesive is obtained.

[0051] Comparative Example 2

[0052] The difference from Example 1 is that no pentaerythritol rosin ester is added, and the rest is the same. A pressure-sensitive adhesive is obtained.

[0053] Comparative Example 3

[0054] The difference from Example 1 is that methyl methacrylate and isobornyl acrylate are not added, and the rest is the same. A pressure-sensitive adhesive is obtained.

[0055] Comparative Example 4

[0056] The difference from Example 1 is that 8 parts of octavinyl cage silsesquioxane are used, and the rest is the same. A pressure-sensitive adhesive is obtained.

[0057] The performance of the pressure-sensitive adhesives obtained in the embodiments and comparative examples was tested as follows:

[0058] Peel strength: Referring to GB / T 2792-2014, the pressure-sensitive adhesive is evenly coated on a polyethylene film as a sample, and its 180° peel strength with a steel plate is tested. For each embodiment or comparative example, 10 samples are prepared and divided into a conventional group and a weathering group. The conventional group is directly tested; the weathering group is subjected to the same test after weathering treatment to simulate the change in peel strength under harsh conditions. The weathering treatment method is: (1) high temperature-water spraying cycle 80 times, each operation is: heating to 60°C, standing for 3 hours, and then watering for 1 hour, the watering temperature is 10°C, and the watering volume is 0.5L / m 2 ·min, and then stand for 1 hour after watering; (2) 20 heating-freezing cycles, each operation is: heating to 50°C within 3 hours, standing for 5 hours, then cooling to -20°C at a constant speed within 4 hours, and standing for 12 hours. The test results are averaged.

[0059] Stickiness: Refer to GB / T 32368-2015.

[0060] High temperature resistance: Apply the pressure-sensitive adhesive evenly on the glass, store it in a 200℃ environment for 8 hours, then peel it off and observe the residual adhesive.

[0061] High humidity and high temperature resistance: Apply the pressure-sensitive adhesive evenly on the glass, store it in an environment with a temperature of 85°C and a relative humidity of 85% for 48 hours, then peel it off and observe the residual adhesive.

[0062] The test results are shown in Table 1.

[0063] Table 1

[0064]

[0065] As can be seen from Table 1, the absence or excessive addition of olefin-based cage silsesquioxane will affect the performance of the pressure-sensitive adhesive of the present invention. Olefin-based cage silsesquioxane can improve the adhesion, high temperature resistance and weather resistance of the pressure-sensitive adhesive, and extend the service life of the product under harsh conditions. Rosin pentaerythritol ester can improve the adhesion and peel strength of the pressure-sensitive adhesive. Hard monomers have a great influence on the high temperature resistance of the pressure-sensitive adhesive. The pressure-sensitive adhesive of the present invention has good high temperature and humidity resistance and weather resistance, high peel strength, good adhesion, and can be applied to a variety of fields.

[0066] In this specification, each embodiment is described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the embodiments can be referred to each other. For the scheme disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant parts can be referred to the method part.

[0067] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A highly weather-resistant pressure-sensitive adhesive, It is characterized in that The raw materials are as follows: 30-40 parts of soft monomer, 5-10 parts of hard monomer, 1-3 parts of functional monomer, 50-80 parts of solvent, 1-5 parts of olefin cage silsesquioxane, 1-3 parts of rosin pentaerythritol ester, 0.5-1 parts of initiator and 0.5-0.8 parts of curing agent.

2. A highly weather-resistant pressure-sensitive adhesive according to claim 1, It is characterized in that The soft monomer is selected from one or more of butyl acrylate, isooctyl methacrylate, ethyl acrylate, lauryl acrylate and butyl methacrylate.

3. A highly weather-resistant pressure-sensitive adhesive according to claim 1, It is characterized in that The hard monomer is a mixture of methyl methacrylate and isobornyl acrylate.

4. A highly weather-resistant pressure-sensitive adhesive according to claim 3, It is characterized in that The mass ratio of methyl methacrylate to isobornyl acrylate is 3-5:

1.

5. The highly weather-resistant pressure-sensitive adhesive according to claim 1, It is characterized in that The functional monomer is selected from one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxyethyl methacrylate.

6. A highly weather-resistant pressure-sensitive adhesive according to claim 1, It is characterized in that The olefin-based cage-type silsesquioxane is selected from one or more of vinyl-cage-type silsesquioxane and methacryl-cage-type silsesquioxane.

7. A highly weather-resistant pressure-sensitive adhesive according to claim 1, It is characterized in that The solvent is selected from one or more of toluene, ethyl acetate and butanone.

8. The highly weather-resistant pressure-sensitive adhesive according to claim 1, It is characterized in that The initiator is selected from one or more of dibenzoyl peroxide, dilauroyl peroxide, dicumyl peroxide, azobisisobutyronitrile and azobisisoheptylnitrile.

9. The highly weather-resistant pressure-sensitive adhesive according to claim 1, It is characterized in that The curing agent is selected from one or more of triethylenediamine, zinc isooctanoate, and aluminum triacetylacetonate.

10. A method for preparing a highly weather-resistant pressure-sensitive adhesive according to any one of claims 1 to 9, It is characterized in that The following steps are involved: (1) Add soft monomer, hard monomer, functional monomer and solvent into a reaction vessel, introduce nitrogen to expel air, add initiator, raise the temperature to 70-80°C, and react for 4-6 hours; (2) Continue to add olefin-based cage-type silsesquioxane and rosin pentaerythritol ester, react for 2-3 hours, cool to room temperature, add curing agent, stir for 0.5-1 hour, and obtain a pressure-sensitive adhesive.

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