阅读说明：本技术 一种丙烯酸酯乳液压敏胶的制备方法 (Preparation method of acrylate emulsion pressure-sensitive adhesive ) 是由 刘若鹏 赵治亚 肖成伟 于 2019-04-28 设计创作，主要内容包括：本发明提供一种丙烯酸酯乳液压敏胶的制备方法,包括以下步骤：S1将乳化剂与碳酸氢钠水溶液共混得到混合溶液A；S2制备包括软单体、硬单体和功能单体的混合单体B；S3制备氧化石墨烯水溶液,将氧化石墨烯水溶液与混合单体B共混得到溶液C；S4分批向混合溶液A中加入溶液C和引发剂,在60℃～100℃反应2-10h,然后冷却至室温,调节溶液PH值至中性,过滤得到乳液D；S5向乳液D中分别加入增粘树脂、交联单体、润湿剂和消泡剂,并用去离子水调整乳液固含量,即得到本发明所述丙烯酸酯乳液压敏胶。本发明中压敏胶老化前后的可剥离性好,剥离后基材表面无明显残胶现象；且压敏胶为水性体系,使用安全,环保。(The invention provides a preparation method of an acrylate emulsion pressure-sensitive adhesive, which comprises the following steps: s1, blending an emulsifier and a sodium bicarbonate water solution to obtain a mixed solution A; s2, preparing a mixed monomer B comprising a soft monomer, a hard monomer and a functional monomer; s3, preparing a graphene oxide aqueous solution, and blending the graphene oxide aqueous solution and the mixed monomer B to obtain a solution C; s4, adding the solution C and an initiator into the mixed solution A in batches, reacting for 2-10h at 60-100 ℃, then cooling to room temperature, adjusting the pH value of the solution to be neutral, and filtering to obtain emulsion D; s5, respectively adding tackifying resin, crosslinking monomer, wetting agent and defoaming agent into the emulsion D, and adjusting the solid content of the emulsion by using deionized water to obtain the acrylate emulsion pressure-sensitive adhesive. The pressure-sensitive adhesive has good strippability before and after aging, and no obvious adhesive residue phenomenon exists on the surface of a base material after stripping; and the pressure-sensitive adhesive is an aqueous system, is safe to use and is environment-friendly.)

1. The preparation method of the acrylate emulsion pressure-sensitive adhesive is characterized by comprising the following steps:

s1, blending an emulsifier and a sodium bicarbonate water solution to obtain a mixed solution A;

s2, preparing a mixed monomer B comprising a soft monomer, a hard monomer and a functional monomer;

s3, preparing a graphene oxide aqueous solution, and blending the graphene oxide aqueous solution and the mixed monomer B to obtain a solution C;

s4, adding the solution C and an initiator into the mixed solution A in batches, reacting for 2-10 hours at the temperature of 60-100 ℃, then cooling to room temperature, adjusting the pH value of the solution to be neutral, and filtering to obtain emulsion D;

S5, respectively adding tackifying resin, crosslinking monomer, wetting agent and defoaming agent into the emulsion D, and adjusting the solid content of the emulsion by using deionized water to obtain the acrylate emulsion pressure-sensitive adhesive.

2. The preparation method according to claim 1, wherein the concentration of the graphene oxide aqueous solution is 5mg/ml to 20mg/ml, and the mass ratio of the graphene oxide aqueous solution to the mixed monomer B is (25 to 35): 100.

3. the production method according to claim 1, wherein the soft monomer in the mixed monomer B: hard monomer: the functional monomer is (65-85): (10-15): (3-5).

4. The method of claim 1, wherein the soft monomers comprise butyl acrylate and isooctyl acrylate; the hard monomers include methyl methacrylate and styrene; the functional monomers include acrylic acid and hydroxyethyl acrylate.

5. The method of claim 1, wherein the crosslinking monomer is acetoacetoxyethyl methacrylate.

6. The method according to claim 1, wherein the emulsion D: tackifying resin: crosslinking monomer: wetting agent: the defoaming agent is (120-180): (15-20): (2-4): (0.01-0.5): (0.2 to 1).

7. The preparation method according to claim 1, wherein the emulsifier is a composite emulsifier prepared by mixing sodium dodecyl sulfate and alkylphenol polyoxyethylene ether according to a molar ratio of 1:1, the mass fraction of sodium bicarbonate in the sodium bicarbonate aqueous solution is 2.5%, and the mass ratio of the composite emulsifier to the sodium bicarbonate aqueous solution is 1: (15-40).

8. The preparation method of claim 1, wherein the step S4 is specifically to slowly add 0.1 to 0.5 part of the mixed solution C into the mixed solution a, gradually add 0.2 to 0.4 part of ammonium persulfate dropwise after stirring, so that the whole system reacts at 75 to 85 ℃, blue light appears in the system, the rest of the mixed monomer and ammonium persulfate are added dropwise after 30min, the whole dropwise adding process is completed within 2 to 4 hours, the temperature of the system is raised to 90 ℃ after the dropwise adding is completed, the temperature-preserving reaction is carried out for 30min, then cooling is carried out, after cooling to room temperature, the pH of the system is adjusted to be neutral by using ammonia water, and then filtering is carried out by using a 200-mesh filter bag, so as to obtain the emulsion D.

9. The method of claim 1, wherein the emulsion at step S5 has a solids content of 45% to 60%.

10. The acrylate emulsion pressure-sensitive adhesive obtained by the preparation method according to any one of claims 1 to 9.

[ technical field ] A method for producing a semiconductor device

The invention relates to the technical field of high polymer materials, in particular to a preparation method of an acrylate emulsion pressure-sensitive adhesive.

[ background of the invention ]

The acrylate pressure-sensitive adhesive has the excellent performances of no need of adding an anti-aging agent, good bonding strength, good transparency, medium resistance, no phase separation, no migration and the like, and is the most widely applied pressure-sensitive adhesive in the current market. However, in the actual use process of the existing acrylate pressure-sensitive adhesive in the market, after the pressure-sensitive adhesive is bonded on the surface of the bonded material, the pressure-sensitive adhesive is generally peeled off after a period of time, which is only a few minutes as short, and the long pressure-sensitive adhesive is more than 1 year along with the increase of the use time, the pressure-sensitive adhesive is difficult to peel off and the problem of adhesive residue is very easy to occur in the peeling process, the surface of the bonded material is damaged due to strong peeling, and the pressure-sensitive adhesive remained on the surface of the bonded material after peeling can not be easily removed, so that the aesthetic property of the surface of the material is seriously affected, and the pollution of the bonded material is also caused.

Researches show that the peeling difficulty of the acrylate pressure-sensitive adhesive and the residual adhesive in the peeling process are caused by three reasons, wherein the most common reason is that the peeling strength of the pressure-sensitive adhesive changes after a period of time, the pressure-sensitive adhesive is generally peeled off after a period of time after being adhered to the surface of an adhered material, the peeling strength is only a few minutes as short, and the peeling strength of the pressure-sensitive adhesive is more than 1 year as long as the period of time, the peeling strength of the pressure-sensitive adhesive is increased along with the time, and the peeling strength is usually fast first and slow later and finally tends to be stable. When the peel strength rises to exceed the cohesive strength or adhesive force, cohesive failure or adhesive failure occurs, resulting in adhesive residue. Another reason is the aging of the pressure-sensitive adhesive, which belongs to a high molecular polymer, and after being heated or subjected to long-term ultraviolet irradiation, the macromolecular chains of the pressure-sensitive adhesive are broken, the average molecular mass is reduced, the cohesive strength is reduced, and further cohesive failure occurs. Furthermore, compatibility with the surface material of the material to be bonded is also an important factor in causing adhesive residue. With the lapse of time, the pressure-sensitive adhesive and the surface of the adherend are gradually fused due to the compatibility phenomenon, resulting in an increase in peel strength, resulting in cohesive failure or adhesive failure; or part of the small molecular substances in the pressure-sensitive adhesive layer are compatible with the protected surface, so that the small molecular substances migrate from the pressure-sensitive adhesive to the protected surface to form migration residues.

[ summary of the invention ]

In order to solve the technical problems, the invention provides a preparation method of an acrylate emulsion pressure-sensitive adhesive, which comprises the following steps: s1, blending an emulsifier and a sodium bicarbonate water solution to obtain a mixed solution A; s2, preparing a mixed monomer B comprising a soft monomer, a hard monomer and a functional monomer; s3, preparing a graphene oxide aqueous solution, and blending the graphene oxide aqueous solution and the mixed monomer B to obtain a solution C; s4, adding the solution C and an initiator into the mixed solution A in batches, reacting for 2-10h at 60-100 ℃, then cooling to room temperature, adjusting the pH value of the solution to be neutral, and filtering to obtain emulsion D; s5, respectively adding tackifying resin, crosslinking monomer, wetting agent and defoaming agent into the emulsion D, and adjusting the emulsion solid with deionized water to obtain the acrylate emulsion pressure-sensitive adhesive. According to the invention, graphene oxide is added into the acrylate emulsion pressure-sensitive adhesive, and the anti-aging performance of the acrylic resin is greatly improved by utilizing the good thermal stability, ultraviolet resistance and oxidation resistance of the graphene oxide; strong interface interaction can occur between the graphene oxide and the acrylate matrix, so that the mobility of polymer molecular chains is deteriorated, the cohesive strength and the creep resistance of the pressure-sensitive adhesive are enhanced, the strippability before and after aging is good, and no obvious adhesive residue phenomenon exists on the surface of a base material after stripping; the acrylate emulsion pressure-sensitive adhesive is an aqueous system, does not use a large amount of volatile organic solvents, and is safe and environment-friendly to use.

In some embodiments of the present invention, the concentration of the graphene oxide aqueous solution is 0.1g/ml to 10g/ml, and the mass ratio of the graphene oxide aqueous solution to the mixed monomer B is (25 to 35): 100.

in some embodiments of the invention, the soft monomer: hard monomer: the functional monomer is (65-85): (10-15): (3-5).

In some embodiments of the invention, the soft monomers include butyl acrylate and isooctyl acrylate; the hard monomers include methyl methacrylate and styrene; the functional monomers include acrylic acid and hydroxyethyl acrylate.

In some embodiments of the invention, the tackifying resin is a rosin tackifying resin and the crosslinking monomer is acetoacetoxyethyl methacrylate. According to the invention, by adding a proper amount of crosslinking monomer, the cohesive force of the pressure-sensitive adhesive is improved, and the probability of adhesive residue of the pressure-sensitive adhesive is greatly reduced.

In some embodiments of the invention, the emulsion D: tackifying resin: crosslinking monomer: wetting agent: the defoaming agent is (120-180): (15-20): (2-4): (0.01-0.5): (0.2 to 1). Through the proportioning design, the polymer has proper glass transition temperature (such as minus 30 ℃ to minus 15 ℃), initial viscosity of 19# to 20# and permanent viscosity of 1.2mm to 1.8mm, and the proper glass transition temperature can improve the wettability of the pressure-sensitive adhesive on the surface of a base material on one hand, so that the adhesive property of the pressure-sensitive adhesive is improved, the pressure-sensitive adhesive is easy to peel off, and on the other hand, the polymer has good cohesive strength, and the residual adhesive is not easy to be left during peeling off; the proper initial adhesion, permanent adhesion and glass transition temperature are beneficial to improving the bonding performance and the strippability of the pressure-sensitive adhesive, thereby prolonging the service life of the material.

In some embodiments of the present invention, the emulsifier is an anionic/nonionic complex emulsifier, such as a complex emulsifier prepared by mixing Sodium Dodecyl Sulfate (SDS) and alkylphenol ethoxylate (OP-10) in a molar ratio of 1: 1. The proper amount of the anionic/nonionic composite emulsifier greatly improves the interface energy of a system when water is used as a solvent, reduces the particle size of the emulsion, and improves the dispersion degree of monomers, so that the prepared emulsion has moderate viscosity and the pressure-sensitive adhesive has good physical properties such as permanent viscosity, initial viscosity and the like.

In some embodiments of the present invention, the mass fraction of sodium bicarbonate in the aqueous sodium bicarbonate solution is 2.5%, and the mass ratio of the emulsifier to the aqueous sodium bicarbonate solution is 1: (15-40).

In some embodiments of the invention, the step S4 includes slowly adding 0.1 to 0.5 part of the mixed solution C into the mixed solution a, gradually adding 0.2 to 0.4 part of ammonium persulfate dropwise after stirring to allow the whole system to react at 75 to 85 ℃, so that blue light appears in the system, beginning to dropwise add the remaining mixed monomer and ammonium persulfate after 30min, controlling the whole dropwise adding process to be completed within 2 to 4 hours, raising the temperature of the system to 90 ℃ after the dropwise adding is completed, performing a heat preservation reaction for 30min, then beginning to cool, adjusting the pH of the system to be neutral by using ammonia water after cooling to room temperature, and then filtering by using a 200-mesh filter bag to obtain the emulsion D.

In some embodiments of the present invention, the emulsion solid content in the step S5 is 45% to 60%.

The invention also discloses the acrylate emulsion pressure-sensitive adhesive prepared by the preparation method.

According to the preparation method of the acrylate emulsion pressure-sensitive adhesive, the graphene oxide is added into the acrylate emulsion pressure-sensitive adhesive, the ageing resistance of the acrylic resin is greatly improved by utilizing the good thermal stability, ultraviolet resistance and oxidation resistance of the graphene oxide, the cohesive strength and creep resistance of the pressure-sensitive adhesive are increased, the strippability before and after ageing is good, and no obvious adhesive residue phenomenon exists on the surface of a base material after stripping.

[ detailed description ] embodiments

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.