CN116023582A - Low-viscosity high-temperature-resistant acrylate pressure-sensitive adhesive and preparation method thereof - Google Patents

Abstract

The invention provides a low-viscosity high-temperature-resistant acrylate pressure-sensitive adhesive which comprises the following raw materials in parts by weight: 25-45 parts of soft monomer; 5-20 parts of hard monomer; 1-8 parts of functional monomer; 0.3-0.6 part of initiator; 35-65 parts of solvent; 0.1-0.5 part of cross-linking agent. The invention also relates to a preparation method thereof. The prepared acrylic acid ester pressure-sensitive adhesive has the advantages of high strength, good toughness, strong weather resistance, simple process and the like.

Description

Low-viscosity and high-temperature-resistant acrylate pressure-sensitive adhesive and preparation method thereof

technical field

The invention relates to the field of pressure-sensitive adhesives, in particular to a low-viscosity and high-temperature-resistant acrylate pressure-sensitive adhesive and a preparation method thereof.

Background technique

Adhesive products have the characteristics of simple use and strong design, and their applications in electronic products are becoming more and more diversified. Among them, acrylate pressure-sensitive adhesives are widely used. Pressure-sensitive adhesive is an adhesive that can stick to the adherend with only slight pressure without any other external conditions such as temperature and pressure.

Since the surface of some electronic products is susceptible to contact pollution or scratches during handling and use, a protective film is usually used to cover the surface to protect it from damage and pollution, so a low-adhesive protective film needs to be attached; at the same time Electronic devices will release heat more or less during use; in addition, most of the electronic device manufacturing processes include soldering methods, which requires tape products to have better high temperature resistance, usually through the wettability and peel strength of the tape at high temperatures to reflect.

The patent of publication number CN102516890A discloses a high-temperature-resistant acrylate adhesive. Its monomers and auxiliary components are complex, containing inorganic fillers and rubber, which are not suitable for variable control; A polyacrylate pressure-sensitive adhesive composition with good initial adhesion, oil resistance, weather resistance and high-temperature resistance, but poor temperature resistance; the patent of publication number CN106398600A discloses a high-temperature-resistant solvent-type acrylate pressure-sensitive adhesive, It introduces phenyl-containing monomers and silicon-fluorine elements, and the cost is relatively high.

Therefore, it is necessary to provide a low-viscosity high-temperature-resistant acrylate pressure-sensitive adhesive and a preparation method thereof to solve the above-mentioned problems.

Contents of the invention

In order to overcome the deficiencies in the prior art, the first object of the present invention is to provide a low-viscosity high temperature resistant acrylate pressure-sensitive adhesive, comprising the following raw materials in parts by weight:

Preferably, the soft monomer is at least one of 2-ethylhexyl acrylate, butyl acrylate, and ethyl acrylate.

Preferably, the hard monomer is at least one of acrylamide, methyl methacrylate, methyl acrylate, and vinyl acetate.

Preferably, the functional monomer is at least one of acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, and N-methylolacrylamide.

Preferably, the initiator is at least one of benzoyl peroxide, azobisisobutyronitrile and azobisisoheptanonitrile.

Preferably, the solvent is at least one of toluene, ethyl acetate, butyl acetate, and butanone.

Preferably, the crosslinking agent is at least one of epoxy crosslinking agent and isocyanate crosslinking agent.

The second object of the present invention is to provide a method for preparing the above-mentioned low-viscosity and high-temperature-resistant acrylate pressure-sensitive adhesive, comprising the following steps:

Step 1: Throw soft monomers, hard monomers, functional monomers, solvents and crosslinking agents in parts by weight into the experimental device; while stirring, feed the air in the nitrogen removal device and add 0.1-0.3 Parts by mass of initiator, react for 2H at about 66°C;

Step 2: Add 0.1-0.3 parts by mass of initiator, control the temperature around 74°C, and react for 2H;

Step 3: Add 0.1-0.3 parts by mass of an initiator, continue to react for 3 hours at a temperature higher than 78° C., and cool to obtain the target pressure-sensitive adhesive.

Compared with the prior art, the beneficial effect of the present invention is that: the present invention provides a low-viscosity and high-temperature-resistant acrylate pressure-sensitive adhesive, including the following raw materials in parts by weight: 25-45 parts of soft monomer; 5-20 parts of hard monomer; 1-8 parts of functional monomer; 0.3-0.6 parts of initiator; 35-65 parts of solvent; 0.1-0.5 parts of crosslinking agent. The present invention also relates to its preparation method. The acrylate pressure-sensitive adhesive thus prepared has the advantages of high strength, good toughness, strong weather resistance, simple process and the like.

The above description is only an overview of the technical solutions of the present invention. In order to understand the technical means of the present invention more clearly and implement them according to the contents of the description, the preferred embodiments of the present invention will be described in detail below. The specific embodiment of the present invention is given in detail by the following examples.

Detailed ways

In the following, the present invention will be further described in conjunction with specific embodiments. It should be noted that, on the premise of not conflicting, the various embodiments or technical features described below can be combined arbitrarily to form new embodiments.

In order to overcome the deficiencies of existing pressure-sensitive adhesives, the present invention relates to a low-viscosity and high-temperature-resistant acrylate pressure-sensitive adhesive, comprising the following raw materials in parts by weight:

The pressure-sensitive adhesive prepared in this way has the advantages of high strength, good toughness, strong weather resistance, and simple process, so that it can be widely used in various industries; ranging from aerospace, automobiles, ships, railways and construction, to small electronic products , household instruments, toys and handicrafts and other industries; Benming’s two-component acrylic adhesive mainly solves the problem that the current acrylic protective film products have a significant increase or decrease in viscosity after being baked at high temperature, and can be used no matter at room temperature or at high temperature. It has a good bonding effect, and there will be no degumming, residual glue and other phenomena.

Add a curing agent to the pressure-sensitive adhesive and spread it evenly on the PET substrate. After the acrylate adhesive is completely cured, attach this protective film to the steel plate and bake it in an environment of 180°C for 24 hours. , There is no obvious change in viscosity, and there will be no degumming, residual glue and other phenomena.

The pressure-sensitive adhesive of the present invention has good cohesion, and under the premise of temperature resistance, the viscosity of the obtained protective film product can be adjusted appropriately. After the protective film made of the pressure-sensitive adhesive is baked at 180°C for 24 hours, the viscosity has no obvious change; after experiencing high temperature and high humidity environment, the viscosity remains basically unchanged; and after baking at 180°C for 24 hours There is no residual glue and degumming phenomenon on the steel plate.

In some embodiments, the soft monomer is at least one of 2-ethylhexyl acrylate, butyl acrylate, and ethyl acrylate, mainly to provide wettability and viscosity, and enhance flexibility and extensibility.

In some embodiments, the hard monomer is at least one of acrylamide, methyl methacrylate, methyl acrylate, and vinyl acetate, and is mainly copolymerized with an adhesive monomer to increase the glass transition temperature and cohesive properties , has a special effect on the improvement of adhesion, water resistance, transparency and manufacturability, and it can increase the hardness and tensile strength of the copolymer resin.

In some embodiments, the functional monomer is at least one of acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, and N-methylolacrylamide, mainly to provide crosslinking , improve cohesive strength and adhesion, accelerate polymerization reaction speed, and improve polymerization stability.

In some embodiments, the initiator is at least one of benzoyl peroxide, azobisisobutyronitrile, and azobisisoheptanonitrile. The thermal decomposition of the initiator mainly produces only one kind of free radical, and the decomposition The temperature is relatively low.

In some embodiments, in order to ensure the dissolution effect of the raw materials, the solvent is at least one of toluene, ethyl acetate, butyl acetate, and butanone.

In some embodiments, the crosslinking agent is at least one of epoxy crosslinking agent and isocyanate crosslinking agent.

The present invention also relates to a method for preparing a low-viscosity and high-temperature-resistant acrylate pressure-sensitive adhesive, comprising the following steps:

Step 1: Throw soft monomers, hard monomers, functional monomers, 0.1-0.3 mass parts initiators, solvents and crosslinking agents in parts by weight into the experimental device; while stirring, feed into the nitrogen removal device In the air, add part of the initiator, and react for 2H at about 66°C;

Step 2: Add 0.1-0.3 parts by mass of initiator, control the temperature around 74°C, and react for 2H;

Step 3: Add 0.1-0.3 parts by mass of an initiator, continue to react for 3 hours at a temperature higher than 78° C., and cool to obtain the target pressure-sensitive adhesive.

Add a curing agent to the acrylate pressure-sensitive adhesive and spread it evenly on the PET substrate. After the acrylate adhesive is completely cured, attach this protective film to the steel plate and bake it in an environment of 180°C After 24 hours, there will be no significant change in viscosity, and there will be no phenomenon of degumming and residual glue.

Embodiment one

Throw 40 parts by weight of soft monomer isooctyl acrylate in experimental device, 10 parts by weight of vinyl acetate of hard monomer, 1.5 parts by weight of methyl methacrylate of hard monomer, 3 weight parts of functional monomer acrylic acid Parts, solvent ethyl acetate 18 weight parts, solvent butanone 27 weight parts. While stirring, feed the air in the nitrogen removal device, add 0.1 parts by weight of azobisisobutyronitrile, and react for 2 hours at about 66°C; add 0.2 parts by weight of azobisisobutyronitrile, control the temperature at around 74°C, and react 2H; add 0.2 parts by weight of azobisisobutyronitrile, the temperature is higher than 78°C, continue to react for 3H, and cool to obtain the target adhesive.

Embodiment two

35 parts by weight of the soft monomer isooctyl acrylate in the experimental device, 5 parts by weight of the soft monomer butyl acrylate, 10 parts by weight of the hard monomer vinyl acetate, and 10 parts by weight of the hard monomer methyl methacrylate. 1.5 parts by weight, 3 parts by weight of functional monomer acrylic acid, 18 parts by weight of ethyl acetate as a solvent, and 27 parts by weight as a solvent butanone. While stirring, feed the air in the nitrogen removal device, add 0.1 parts by weight of azobisisobutyronitrile, and react for 2 hours at about 66°C; add 0.2 parts by weight of azobisisobutyronitrile, control the temperature at around 74°C, and react 2H; add 0.2 parts by weight of azobisisobutyronitrile, the temperature is higher than 78°C, continue to react for 3H, and cool to obtain the target adhesive.

Embodiment Three

Throw 35 parts by weight of soft monomer isooctyl acrylate in experimental device, 13 parts by weight of hard monomer vinyl acetate, 3.5 parts by weight of hard monomer methyl methacrylate, and 3 parts by weight of functional monomer acrylic acid Parts, solvent ethyl acetate 18 weight parts, solvent butanone 27 weight parts. While stirring, feed the air in the nitrogen removal device, add 0.1 parts by weight of azobisisobutyronitrile, and react for 2 hours at about 66°C; add 0.2 parts by weight of azobisisobutyronitrile, control the temperature at around 74°C, and react 2H; add 0.2 parts by weight of azobisisobutyronitrile, the temperature is higher than 78°C, continue to react for 3H, and cool to obtain the target adhesive.

Embodiment Four

30 parts by weight of the soft monomer isooctyl acrylate in the experimental device, 5 parts by weight of the soft monomer butyl acrylate, 13 parts by weight of the hard monomer vinyl acetate, and 13 parts by weight of the hard monomer methyl methacrylate. 3.5 parts by weight, 3 parts by weight of functional monomer acrylic acid, 18 parts by weight of ethyl acetate as a solvent, and 27 parts by weight as a solvent butanone. Pass the air in the nitrogen removal device, add 0.1 parts by weight of azobisisobutyronitrile, react for 2H at about 66°C; add 0.2 parts by weight of azobisisobutyronitrile, control the temperature at around 74°C, and react for 2H; add azo 0.2 parts by weight of diisobutyronitrile, at a temperature higher than 78° C., continue to react for 3 hours, and cool to obtain the target adhesive.

Embodiment five

Throw 30 parts by weight of soft monomer isooctyl acrylate in experimental device, 10 parts by weight of vinyl acetate of hard monomer, 5 parts by weight of methyl methacrylate of hard monomer, 7.5 parts by weight of functional monomer acrylic acid Parts, solvent ethyl acetate 25 parts by weight, solvent butanone 22 parts by weight. While stirring, feed the air in the nitrogen removal device, add 0.1 parts by weight of azobisisobutyronitrile, and react for 2 hours at about 66°C; add 0.2 parts by weight of azobisisobutyronitrile, control the temperature at around 74°C, and react 2H; add 0.2 parts by weight of azobisisobutyronitrile, the temperature is higher than 78°C, continue to react for 3H, and cool to obtain the target adhesive.

Embodiment six

Throw 25 parts by weight of soft monomer isooctyl acrylate in experimental device, 12 parts by weight of vinyl acetate of hard monomer, 2.5 parts by weight of methyl methacrylate of hard monomer, 10 parts by weight of functional monomer acrylic acid Parts, solvent ethyl acetate 40 weight parts, solvent butanone 10 weight parts. While stirring, feed the air in the nitrogen removal device, add 0.1 parts by weight of azobisisobutyronitrile, and react for 2 hours at about 66°C; add 0.2 parts by weight of azobisisobutyronitrile, control the temperature at around 74°C, and react 2H; add 0.2 parts by weight of azobisisobutyronitrile, the temperature is higher than 78°C, continue to react for 3H, and cool to obtain the target adhesive.

Comparative example one

27 mass parts of soft monomer isooctyl acrylate, 14 mass parts of soft monomer butyl acrylate, 4 mass parts of hard monomer methyl acrylate, and 5 mass parts of functional monomer hydroxyethyl acrylate are thrown into the experimental device in parts by weight. Parts by mass, functional monomer acrylic acid 2.5 parts by mass, solvent ethyl acetate 35 parts by mass, solvent butanone 12 parts by mass. Under the condition of stirring, pass the air in the nitrogen removal device, add 0.1 mass part of azobisisobutyronitrile, and react for 2 hours at about 66 °C; add 0.2 mass part of azobisisobutyronitrile, control the temperature at around 74 °C, and react 2H; add 0.2 parts of azobisisobutyronitrile, the temperature is higher than 78°C, continue to react for 3H, cool down, and add a diluent solvent to obtain the target adhesive.

Comparative example two

35 parts by weight of the soft monomer isooctyl acrylate in the experimental device, 0.1 parts by weight of the functional monomer hydroxyethyl acrylate, 10 parts by weight of the hard monomer methyl acrylate, and the shrinkage of the functional monomer methacrylic acid 1.4 parts by mass of glyceride, 3 parts by mass of functional monomer acrylic acid, 45 parts by mass of ethyl acetate as a solvent, and 5 parts by mass of solvent. While stirring, feed the air in the nitrogen removal device, add 0.1 part of azobisisobutyronitrile, react for 2H at about 66°C; add 0.2 part of azobisisobutyronitrile, control the temperature at around 74°C, and react for 2H; Add 0.2 parts of azobisisobutyronitrile, the temperature is higher than 78°C, continue to react for 3 hours, cool down, and add a diluent solvent to obtain the target adhesive.

Comparative example three

Throw 38 parts of soft monomer isooctyl acrylate in the experimental device, 0.1 part of functional monomer hydroxyethyl acrylate, 1.6 parts of hard monomer acrylamide, 5 parts of hard monomer methyl acrylate, soft monomer 5.6 parts of bulk butyl acrylate, 3.2 parts of functional monomer glycidyl methacrylate, 2.6 parts of functional monomer acrylic acid, and 44 parts of solvent ethyl acetate. While stirring, feed the air in the nitrogen removal device, add 0.1 part of azobisisobutyronitrile, react for 2H at about 66°C; add 0.2 part of azobisisobutyronitrile, control the temperature at around 74°C, and react for 2H; Add 0.2 parts of azobisisobutyronitrile, the temperature is higher than 78°C, continue to react for 3 hours, cool down, and add a diluent solvent to obtain the target adhesive.

Comparative example four

Throw 43 parts by weight of soft monomer isooctyl acrylate into the experimental device, 0.1 part of functional monomer hydroxyethyl acrylate, 1.6 parts of hard monomer methyl methacrylate, and 5 parts of hard monomer methyl acrylate , 3 parts of functional monomer glycidyl methacrylate, 2.8 parts of functional monomer acrylic acid, 44 parts of solvent ethyl acetate. While stirring, feed the air in the nitrogen removal device, add 0.1 part of azobisisobutyronitrile, react for 2H at about 66°C; add 0.2 part of azobisisobutyronitrile, control the temperature at around 74°C, and react for 2H; Add 0.2 parts of azobisisobutyronitrile, the temperature is higher than 78°C, continue to react for 3 hours, cool down, and add a diluent solvent to obtain the target adhesive.

Comparative example five

30 parts by weight of the soft monomer isooctyl acrylate in the experimental device, 13 parts by weight of the soft monomer butyl acrylate, 0.1 parts by weight of the functional monomer hydroxyethyl acrylate, and the hard monomer methyl methacrylate 1.6 parts by mass of ester, 5 parts by mass of methyl acrylate as a hard monomer, 3 parts by mass of glycidyl methacrylate as a functional monomer, 2.8 parts by mass of acrylic acid as a functional monomer, 30 parts by mass of ethyl acetate as a solvent, and 14 parts by mass of butanone. Under the condition of stirring, pass the air in the nitrogen removal device, add 0.1 mass part of azobisisobutyronitrile, and react for 2 hours at about 66 °C; add 0.2 mass part of azobisisobutyronitrile, control the temperature at around 74 °C, and react 2H; add 0.2 parts by mass of azobisisobutyronitrile, the temperature is higher than 78°C, continue to react for 3H, cool down, and add a diluent solvent to obtain the target adhesive.

Embodiment 1-6 of the present invention, comparative example 1-5 comparative mode is as follows:

Condition 1:

Examples 1-6 and Comparative Examples 1-5 are all operated according to the following method, the obtained adhesive is mixed with 0.4% epoxy curing agent, the coating substrate is a 50 μm polyester (PET) film, and the thickness of the glue is 25 μm , after baking at 120°C for 2 minutes, attach the release film to obtain a protective film product, put it in a 55°C electric constant temperature blast drying oven for 24 hours, and test the 180° normal temperature peel strength. The test results are shown in Table 1 .

The product aged at 55°C for 24 hours was attached to a steel plate and placed in an environment of 180°C for 24 hours. After cooling, the 180°peel strength and whether there was degumming were tested. The test results are shown in Table 1. Test environment temperature: 23±1℃, humidity: 50±5%.

Table 1 Different embodiment detection performance table 1

Although the embodiment of the present invention has been disclosed as above, it is not limited to the use listed in the specification and implementation, it can be applied to various fields suitable for the present invention, and it can be easily understood by those skilled in the art Therefore, the invention is not limited to the specific details and embodiments shown here, without departing from the general concept defined by the claims and their equivalents.

Claims (8)

1. The low-viscosity high-temperature-resistant acrylate pressure-sensitive adhesive is characterized by comprising the following raw materials in parts by weight:

2. the low-tack, high temperature acrylate pressure sensitive adhesive of claim 1 wherein said soft monomer is at least one of 2-ethylhexyl acrylate, butyl acrylate, ethyl acrylate.

3. The low-tack, high temperature acrylate pressure sensitive adhesive of claim 1 wherein said hard monomer is at least one of acrylamide, methyl methacrylate, methyl acrylate, vinyl acetate.

4. The low-tack, high temperature acrylate pressure sensitive adhesive of claim 1 wherein said functional monomer is at least one of acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl methacrylate, N-methylolacrylamide.

5. The low-tack, high temperature acrylate pressure sensitive adhesive of claim 1 wherein said initiator is at least one of benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile.

6. The low-tack, high temperature acrylate pressure sensitive adhesive of claim 1 wherein said solvent is at least one of toluene, ethyl acetate, butyl acetate, butanone.

7. The low-viscosity, high-temperature-resistant acrylate pressure-sensitive adhesive according to claim 1, wherein the crosslinking agent is at least one of an epoxy crosslinking agent and an isocyanate crosslinking agent.

8. The method for preparing the low-viscosity high-temperature-resistant acrylate pressure-sensitive adhesive according to claim 1, comprising the following steps:

step one: soft monomer, hard monomer, functional monomer, solvent and cross-linking agent are added into the experimental device in parts by weight; under the condition of stirring, introducing air in a nitrogen removal device, adding 0.1-0.3 part by mass of initiator, and reacting for 2H at about 66 ℃;

step two: adding 0.1-0.3 part by mass of initiator, controlling the temperature to be near 74 ℃, and reacting for 2H;

step three: adding 0.1-0.3 part by mass of initiator, and continuing to react for 3H at the temperature of more than 78 ℃, and cooling to obtain the target pressure-sensitive adhesive.