阅读说明：本技术 一种耐高温溶剂型丙烯酸酯压敏胶及其制备方法 (High-temperature-resistant solvent type acrylate pressure-sensitive adhesive and preparation method thereof ) 是由 蹇成 樊勤海 樊秋实 于 2020-12-22 设计创作，主要内容包括：本发明提出的一种耐高温丙烯酸酯压敏胶,按重量份数计包括以下组分：软单体60-70份、硬单体20-40份、功能单体1-5份、引发剂0-0.7份、固化剂0-2份、增粘树脂0-6份；其中,溶剂为乙酸乙酯溶液；通过调整功能单体的比例,增加内聚强度和耐高温性能,从而减少了其它助剂的使用,在存储或耐候性测试中不宜出现分层的现象,由于加入了丙烯酰胺,提高了胶体的耐高温性能,而相应的采用了异氰酸酯类固化剂、环氧类交联剂,提高了胶水的内聚强度,也就是说达到了耐高温性能和初粘性能的两者兼容；同时公开了对应的制备方法,其工艺步骤简单,胶带配方的助剂添加类型减少但性能反而有所提升。(The invention provides a high-temperature-resistant acrylate pressure-sensitive adhesive which comprises the following components in parts by weight: 60-70 parts of soft monomer, 20-40 parts of hard monomer, 1-5 parts of functional monomer, 0-0.7 part of initiator, 0-2 parts of curing agent and 0-6 parts of tackifying resin; wherein the solvent is ethyl acetate solution; the cohesive strength and the high-temperature resistance are improved by adjusting the proportion of the functional monomers, so that the use of other auxiliary agents is reduced, the phenomenon of layering is not easy to occur in storage or weather resistance test, the high-temperature resistance of the colloid is improved due to the addition of acrylamide, the cohesive strength of the glue is improved due to the corresponding adoption of an isocyanate curing agent and an epoxy cross-linking agent, namely the compatibility of the high-temperature resistance and the initial adhesion performance is achieved; meanwhile, a corresponding preparation method is disclosed, the process steps are simple, the addition type of the auxiliary agent in the formula of the adhesive tape is reduced, and the performance is improved.)

1. The high-temperature-resistant acrylate pressure-sensitive adhesive is characterized by comprising the following components in parts by weight: 60-70 parts of soft monomer, 20-40 parts of hard monomer, 1-5 parts of functional monomer, 0-0.7 part of initiator, 0-2 parts of curing agent and 0-6 parts of tackifying resin; wherein the solvent is ethyl acetate solution.

2. The high temperature resistant acrylate pressure sensitive adhesive according to claim 1, wherein the hard monomer is one or more of methyl acrylate, vinyl acetate and methyl methacrylate.

3. The high temperature resistant acrylate pressure sensitive adhesive of claim 2, wherein the soft monomer is one or more of isooctyl acrylate and butyl acrylate.

4. The high temperature resistant acrylate pressure sensitive adhesive according to claim 3, wherein the functional monomer is one or more of acrylic acid, hydroxypropyl acrylate, hydroxyethyl acrylate and acrylamide.

5. The high temperature resistant acrylate pressure sensitive adhesive of claim 4 wherein the initiator is dibenzoyl peroxide; the curing agent is isocyanate curing agent; the tackifying resin is modified terpene resin.

6. The high-temperature-resistant acrylate pressure-sensitive adhesive according to claim 5, wherein the adhesive comprises 12 parts of butyl acrylate, 50 parts of isooctyl acrylate, 25 parts of vinyl acetate, 9 parts of methyl acrylate, 2 parts of acrylic acid, 2 parts of hydroxypropyl acrylate, 6 parts of modified terpene resin and 2 parts of isocyanate curing agent.

7. A preparation method of high-temperature-resistant acrylate pressure-sensitive adhesive is characterized in that the component raw materials according to any one of claims 1 to 6 are adopted, and the preparation method comprises the following steps:

s1, adding the weighed hard monomer, soft monomer and ethyl acetate solution into a condensation reflux reaction kettle, gradually heating to 80-82 ℃, and keeping the temperature while stirring;

s2, dropwise adding the functional monomer into a condensation reflux reaction kettle, and slowly dropwise adding an ethyl acetate solution and a half of initiator; simultaneously maintaining the temperature at 80-82 ℃ for 1 h;

s3, dropwise adding the rest of the initiator and the ethyl acetate solution into the condensation reflux reaction kettle, simultaneously heating to 84-88 ℃, and subsequently preserving heat for 3 hours;

s4, after the heat preservation is finished, cooling to room temperature and discharging to obtain an acrylate solution with the solid content of 45-50%;

s5, adding weighed curing agent, tackifying resin and ethyl acetate solution into the acrylic ester solution, and uniformly stirring by a dispersion machine to obtain the acrylic ester pressure sensitive adhesive solution with the solid content of 30-35%.

8. The preparation method of the high temperature resistant acrylate pressure-sensitive adhesive according to claim 7, wherein in S3, the dropping time of the ethyl acetate and the initiator is 2h, and then the temperature is kept at 80-82 ℃ for 1 h.

9. The method for preparing the high-temperature-resistant acrylate pressure-sensitive adhesive according to claim 7, wherein the dropping time in S4 is 1 h.

10. The method for preparing the high temperature resistant acrylate pressure-sensitive adhesive according to claim 7, wherein the acrylate pressure-sensitive adhesive solution is coated on a release film by a coating device, and then is baked in a high temperature oven at 100 ℃ and 120 ℃ for 1-2min, and then a PET film is attached to obtain the acrylate pressure-sensitive adhesive tape.

Technical Field

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

Background

The adhesive products have the characteristics of simple use, strong designability and the like, and are applied to electronic products more and more in a diversified way, wherein the acrylate pressure-sensitive adhesive is widely applied. The pressure-sensitive adhesive is an adhesive which can be adhered to an adherend by only slight pressure without any external conditions such as temperature and pressure. Electronic devices are generally small in size and high in precision, so that the adhesive tape for bonding needs to have high viscosity, and the electronic devices can release heat more or less when in use; in addition, most electronic device manufacturing processes include soldering methods, which requires the tape products to have better high temperature resistance, usually expressed by the wettability and peel strength of the tape at high temperature.

Most of the single solvent type acrylate pressure-sensitive adhesives are prepared by synthesizing soft monomers, the Tg of the monomers is low, and the structure determines that the single solvent type acrylate pressure-sensitive adhesives have poor heat resistance, can become soft at high temperature and cannot be normally used, so that the application of the single solvent type acrylate pressure-sensitive adhesives in more fields is limited to a great extent. In some prior arts, a method for improving compactness of a crosslinked network structure by soft and hard monomers, inorganic fillers and some modified compounds is disclosed, but in this case, a synthesis method is complicated, and the formed pressure-sensitive adhesive has a high Tg, although the high temperature resistance is improved, initial adhesive performance of the adhesive is low; therefore, the compatibility problem of the two is not solved, and a high-temperature-resistant acrylate pressure-sensitive adhesive capable of balancing the performances of the two is urgently needed.

Disclosure of Invention

In order to solve the existing problems, the invention provides the high-temperature-resistant acrylate pressure-sensitive adhesive which is relatively simple in synthesis method, has high-temperature resistance and good initial adhesion performance.

In order to achieve the aim, the invention provides a high-temperature-resistant acrylate pressure-sensitive adhesive which comprises the following components in parts by weight: 60-70 parts of soft monomer, 20-40 parts of hard monomer, 1-5 parts of functional monomer, 0-0.7 part of initiator, 0-2 parts of curing agent and 0-6 parts of tackifying resin; wherein the solvent is ethyl acetate solution.

Preferably, the hard monomer is one or more of methyl acrylate, vinyl acetate and methyl methacrylate.

Preferably, the soft monomer is one or more of isooctyl acrylate and butyl acrylate.

Preferably, the functional monomer is one or more of acrylic acid, hydroxypropyl acrylate, hydroxyethyl acrylate and acrylamide.

Preferably, the initiator is dibenzoyl peroxide; the curing agent is isocyanate curing agent; the tackifying resin is modified terpene resin.

Preferably, the curing agent comprises 12 parts of butyl acrylate, 50 parts of isooctyl acrylate, 25 parts of vinyl acetate, 9 parts of methyl acrylate, 2 parts of acrylic acid, 2 parts of hydroxypropyl acrylate, 6 parts of modified terpene resin and 2 parts of isocyanate curing agent.

Also discloses a preparation method of the high-temperature-resistant acrylate pressure-sensitive adhesive, which adopts the raw materials and comprises the following steps:

s1, adding the weighed hard monomer, soft monomer and ethyl acetate solution into a condensation reflux reaction kettle, gradually heating to 80-82 ℃, and keeping the temperature while stirring;

s2, dropwise adding the functional monomer into a condensation reflux reaction kettle, and slowly dropwise adding an ethyl acetate solution and a half of initiator; simultaneously maintaining the temperature at 80-82 ℃ for 1 h;

s3, dropwise adding the rest of the initiator and the ethyl acetate solution into the condensation reflux reaction kettle, simultaneously heating to 84-88 ℃, and subsequently preserving heat for 3 hours;

s4, after the heat preservation is finished, cooling to room temperature and discharging to obtain an acrylate solution with the solid content of 45-50%;

s5, adding weighed curing agent, tackifying resin and ethyl acetate solution into the acrylic ester solution, and uniformly stirring by a dispersion machine to obtain the acrylic ester pressure sensitive adhesive solution with the solid content of 30-35%.

Preferably, in S3, the dropping time of the ethyl acetate and the initiator is 2h, and then the temperature is kept at 80-82 ℃ for 1 h.

Preferably, in S4, the dropping time is 1 hour.

Preferably, after obtaining the acrylate pressure-sensitive adhesive solution, coating the acrylate pressure-sensitive adhesive solution on a release film through a coating device, baking the release film for 1-2min through a high-temperature oven at the temperature of 100-120 ℃, and attaching a PET film to obtain the acrylate pressure-sensitive adhesive tape.

The invention has the beneficial effects that: the invention provides a high-temperature-resistant acrylate pressure-sensitive adhesive which comprises the following components in parts by weight: 60-70 parts of soft monomer, 20-40 parts of hard monomer, 1-5 parts of functional monomer, 0-0.7 part of initiator, 0-2 parts of curing agent and 0-6 parts of tackifying resin; wherein the solvent is ethyl acetate solution; the cohesive strength and the high-temperature resistance are improved by adjusting the proportion of the functional monomers, so that the use of other auxiliary agents is reduced, the phenomenon of layering is not easy to occur in storage or weather resistance test, the high-temperature resistance of the colloid is improved due to the addition of acrylamide, and the cohesive strength of the glue is improved due to the corresponding adoption of isocyanate curing agents and epoxy crosslinking agents, namely the compatibility of the high-temperature resistance and the initial adhesion performance is achieved; meanwhile, a corresponding preparation method is disclosed, the process steps are simple, the addition type of the auxiliary agent in the formula of the adhesive tape is reduced, and the performance is improved.

Drawings

FIG. 1 is a flow chart of the preparation method of the present invention.

Detailed Description

In order to more clearly describe the present invention, the present invention will be further described with reference to the accompanying drawings.

In the following description, details of general examples are given to provide a more thorough understanding of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. It should be understood that the specific embodiments are illustrative of the invention and are not to be construed as limiting the invention.

It will be understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or groups thereof.

The invention provides a high-temperature-resistant acrylate pressure-sensitive adhesive which comprises the following components in parts by weight: 60-70 parts of soft monomer, 20-40 parts of hard monomer, 1-5 parts of functional monomer, 0.3-0.7 part of initiator, 0-2 parts of curing agent and 0-6 parts of tackifying resin, wherein the solvent is ethyl acetate solution. The hard monomer is one or more of methyl acrylate, vinyl acetate and methyl methacrylate. The soft monomer is one or more of isooctyl acrylate and butyl acrylate. The functional monomer is one or more of acrylic acid, hydroxypropyl acrylate, hydroxyethyl acrylate and acrylamide. The initiator is dibenzoyl peroxide; the curing agent is isocyanate curing agent; the tackifying resin is modified terpene resin. The main reaction is solution polymerization, namely the pressure-sensitive adhesive is prepared by carrying out free radical copolymerization on a soft monomer, a hard monomer and a functional monomer under the condition of mixing and dissolving ethyl acetate which is an initiator, so that when the hard monomer with a high Tg value is selected as a raw material, the pressure-sensitive adhesive with good high temperature resistance can be obtained, but the initial viscosity of the pressure-sensitive adhesive is influenced, and the soft monomer is added into the raw material components; so that the initial tack performance is improved.

As a most preferable example, 12 parts of butyl acrylate, 50 parts of isooctyl acrylate, 25 parts of vinyl acetate, 9 parts of methyl acrylate, 2 parts of acrylic acid, 2 parts of hydroxypropyl acrylate, 6 parts of modified terpene resin and 2 parts of isocyanate curing agent.

Referring to fig. 1, a method for preparing a high temperature resistant acrylate pressure sensitive adhesive, using the above raw materials, includes the following steps:

s1, adding the weighed hard monomer, soft monomer and ethyl acetate solution into a condensation reflux reaction kettle, gradually heating to 80-82 ℃, and keeping the temperature while stirring;

s2, dropwise adding the functional monomer into a condensation reflux reaction kettle, and slowly dropwise adding an ethyl acetate solution and a half of initiator; simultaneously maintaining the temperature at 80-82 ℃ for 1 h;

s3, dropwise adding the rest of the initiator and the ethyl acetate solution into the condensation reflux reaction kettle, simultaneously heating to 84-88 ℃, and subsequently preserving heat for 3 hours;

s4, after the heat preservation is finished, cooling to room temperature and discharging to obtain an acrylate solution with the solid content of 45-50%;

s5, adding weighed curing agent, tackifying resin and ethyl acetate solution into the acrylic ester solution, and uniformly stirring by a dispersion machine to obtain the acrylic ester pressure sensitive adhesive solution with the solid content of 30-35%.

After the acrylate pressure-sensitive adhesive solution is obtained, the acrylate pressure-sensitive adhesive solution is coated on a release film through a coating device, and then the release film is bonded with a PET film after being baked for 1-2min through a high-temperature oven at the temperature of 100-120 ℃ to obtain the acrylate pressure-sensitive adhesive tape.

In the preparation process, two main parts are mainly prepared, namely, firstly, preparing an acrylate solution with solid content of 45-50%, and then, adding other components and a solvent into the acrylate solution to prepare an acrylate pressure sensitive adhesive solution with solid content of 30-35%. Wherein the solvent is ethyl acetate solution, and the addition amount of the solvent is adjusted according to the quality of each step to reach the corresponding solid content.

Example 1

23 parts of butyl acrylate, 68 parts of isooctyl acrylate, 6 parts of methyl methacrylate, 1 part of acrylic acid, 0.25 part of dibenzoyl peroxide, 6 parts of modified terpene resin and 2 parts of isocyanate curing agent;

s1, adding 23 parts of weighed methyl acrylate, 68 parts of butyl acrylate, 6 parts of methyl methacrylate and an ethyl acetate solution into a condensation reflux reaction kettle, gradually heating to 80-82 ℃, and keeping the temperature while stirring;

s2, dropwise adding 1 part of acrylic acid into a condensation reflux reaction kettle, and slowly dropwise adding ethyl acetate and 0.15 part of dibenzoyl peroxide; simultaneously, maintaining the temperature at 80-82 ℃, dropwise adding for 2h, and then preserving the heat at 80-82 ℃ for 1 h;

s3, dropwise adding the remaining 0.15 part of dibenzoyl peroxide and ethyl acetate solution into a condensation reflux reaction kettle for 1h, simultaneously heating to 84-88 ℃, and subsequently preserving heat for 3 h;

s4, after the heat preservation is finished, cooling to room temperature and discharging to obtain an acrylate solution, wherein the acrylate solution with the solid content of 47-49% can be obtained;

s5, adding 2 parts of weighed isocyanate curing agent and 6 parts of modified terpene resin into 47-49% of acrylate solution, uniformly stirring by a dispersion machine to obtain 30-35% of solid content acrylate pressure-sensitive adhesive solution, coating the acrylate pressure-sensitive adhesive solution on a release film by a coating device after obtaining the acrylate pressure-sensitive adhesive solution, baking for 1-2min by a high-temperature oven at the temperature of 100-120 ℃, and attaching a PET film to obtain the sample No. 1 of the acrylate pressure-sensitive adhesive tape.

Example 2

Weighing 12 parts of butyl acrylate, 45 parts of isooctyl acrylate, 30 parts of vinyl acetate, 9 parts of methyl acrylate, 2 parts of acrylic acid, 2 parts of hydroxypropyl acrylate, 0.4 part of dibenzoyl peroxide, 6 parts of modified terpene resin and 2 parts of isocyanate curing agent;

s1, adding 33 parts of weighed vinyl acetate, 9 parts of methyl acrylate, 12 parts of butyl acrylate, 45 parts of isooctyl acrylate and an ethyl acetate solution into a condensation reflux reaction kettle, gradually heating to 80-82 ℃, and keeping the temperature while stirring;

s2, dropwise adding 2 parts of acrylic acid and 2 parts of hydroxypropyl acrylate into a condensation reflux reaction kettle, and slowly dropwise adding part of ethyl acetate and 0.2 part of dibenzoyl peroxide; simultaneously, maintaining the temperature at 80-82 ℃, dropwise adding for 2h, and then preserving the heat at 80-82 ℃ for 1 h;

s3, dropwise adding the remaining 0.2 part of dibenzoyl peroxide and ethyl acetate solution into a condensation reflux reaction kettle for 1h, simultaneously heating to 84-88 ℃, and subsequently preserving heat for 3 h;

s4, after the heat preservation is finished, cooling to room temperature and discharging to obtain an acrylate solution, wherein the acrylate solution with the solid content of 47-49% can be obtained;

s5, adding 2 parts of weighed isocyanate curing agent and 6 parts of modified terpene resin into 47-49% of acrylate solution, uniformly stirring by a dispersion machine to obtain 30-35% of solid content acrylate pressure-sensitive adhesive solution, coating the acrylate pressure-sensitive adhesive solution on a release film by a coating device after obtaining the acrylate pressure-sensitive adhesive solution, baking for 1-2min by a high-temperature oven at the temperature of 100-120 ℃, and attaching a PET film to obtain the No. 2 sample of the acrylate pressure-sensitive adhesive tape.

Example 3

Weighing 12 parts of butyl acrylate, 45 parts of isooctyl acrylate, 30 parts of vinyl acetate, 9 parts of methyl acrylate, 3 parts of acrylic acid, 1 part of acrylamide, 0.4 part of dibenzoyl peroxide, 6 parts of modified terpene resin and 2 parts of isocyanate curing agent;

s1, adding 12 parts of weighed butyl acrylate, 45 parts of isooctyl acrylate, 30 parts of vinyl acetate, 9 parts of methyl acrylate and an ethyl acetate solution into a condensation reflux reaction kettle, gradually heating to 80-82 ℃, and keeping the temperature while stirring;

s2, dropwise adding 2 parts of acrylic acid and 2 parts of hydroxypropyl acrylate into a condensation reflux reaction kettle, and slowly dropwise adding ethyl acetate and 0.2 part of dibenzoyl peroxide; simultaneously, maintaining the temperature at 80-82 ℃, dropwise adding for 2h, and then preserving the heat at 80-82 ℃ for 1 h;

s3, dropwise adding the remaining 0.2 part of dibenzoyl peroxide and ethyl acetate solution into a condensation reflux reaction kettle for 1h, simultaneously heating to 84-88 ℃, and subsequently preserving heat for 3 h;

s4, after the heat preservation is finished, cooling to room temperature and discharging to obtain an acrylate solution, wherein the acrylate solution with the solid content of 47-49% can be obtained;

s5, adding 2 parts of weighed isocyanate curing agent and 6 parts of modified terpene resin into 47-49% of acrylate solution, uniformly stirring by a dispersion machine to obtain 30-35% of solid content acrylate pressure-sensitive adhesive solution, coating the acrylate pressure-sensitive adhesive solution on a release film by a coating device after obtaining the acrylate pressure-sensitive adhesive solution, baking for 1-2min by a high-temperature oven at the temperature of 100-120 ℃, and attaching a PET film to obtain the No. 3 sample of the acrylate pressure-sensitive adhesive tape.

Best mode 4

Weighing 12 parts of butyl acrylate, 50 parts of isooctyl acrylate, 25 parts of vinyl acetate, 9 parts of methyl acrylate, 2 parts of acrylic acid, 2 parts of hydroxypropyl acrylate, 6 parts of modified terpene resin and 1 part of isocyanate curing agent;

s1, adding 12 parts of weighed butyl acrylate, 50 parts of isooctyl acrylate, 25 parts of vinyl acetate, 9 parts of methyl acrylate and an ethyl acetate solution into a condensation reflux reaction kettle, gradually heating to 80-82 ℃, and keeping the temperature while stirring;

s2, dropwise adding 2 parts of acrylic acid and 2 parts of hydroxypropyl acrylate into a condensation reflux reaction kettle, and slowly dropwise adding ethyl acetate and 0.2 part of dibenzoyl peroxide; simultaneously, maintaining the temperature at 80-82 ℃, dropwise adding for 2h, and then preserving the heat at 80-82 ℃ for 1 h;

s3, dropwise adding the remaining 0.2 part of dibenzoyl peroxide and ethyl acetate solution into a condensation reflux reaction kettle for 1h, simultaneously heating to 84-88 ℃, and subsequently preserving heat for 3 h;

s4, after the heat preservation is finished, cooling to room temperature and discharging to obtain an acrylate solution, wherein the acrylate solution with the solid content of 47-49% can be obtained;

s5, adding 2 parts of weighed isocyanate curing agent and 6 parts of modified terpene resin into 47-49% of acrylate solution, uniformly stirring by a dispersion machine to obtain 30-35% of solid content acrylate pressure-sensitive adhesive solution, coating the acrylate pressure-sensitive adhesive solution on a release film by a coating device after obtaining the acrylate pressure-sensitive adhesive solution, baking for 1-2min by a high-temperature oven at the temperature of 100-120 ℃, and attaching a PET film to obtain the No. 4 sample of the acrylate pressure-sensitive adhesive tape.

The functional monomer is added dropwise twice in the preparation process because the polarity of the functional monomer is relatively high, the reactivity is high, and the molecular chain segment of the polymer is not uniform if the functional monomer is added all at once. In the reaction process, the uniform addition of the functional monomer can ensure that the active points are uniformly distributed in the polymer chain segment, thereby being beneficial to the later-stage crosslinking.

The following performance parameters were obtained by performing high temperature resistance, peel strength and annular tack tests on the four samples, as shown in table 1;

TABLE 1

Sample numbering	High temperature resistance (h/150 degree C)	Peel strength (g/inch)	Ring shaped initial adhesive (g/inch)
				Sample 1	＞24	1200	1400
Sample 2	＞24	1300	1500
				Sample 3	＞24	1200	1500
Sample No. 4	＞24	1500	1700

The performance test result shows that the pressure-sensitive adhesive has excellent high-temperature resistance, the high-temperature retention reaches more than 1500min/150 ℃, and the peel strength can reach 1500g/inch to 2000g/inch due to the addition of the modified terpene resin; and the initial adhesion is high and can reach 1500g/inch to 2000g/inch of annular initial adhesion.

The invention has the technical effects that:

1. the cohesive strength and the high-temperature resistance are improved by adjusting the proportion of the functional monomers, so that the use of other auxiliary agents is reduced, and the phenomenon of layering is not easy to occur in storage or weather resistance test;

2. acrylamide is added to improve the high-temperature resistance of the colloid, and the proportion of soft and hard monomers is less adjusted;

3. the peel strength is improved by using tackifying resin, and can reach 1500g/inch to 2000g/inch of the high-peel-strength acrylic pressure-sensitive adhesive;

4. the cohesive strength of the glue is improved by using isocyanate curing agents or epoxy crosslinking agents, and the cohesive strength can reach the same performance index of the high-cohesive-strength acrylic pressure-sensitive adhesive.

The above disclosure is only for a few specific embodiments of the present invention, but the present invention is not limited thereto, and any variations that can be made by those skilled in the art are intended to fall within the scope of the present invention.