阅读说明：本技术 一种水凝胶型临时粘合剂及其制备方法和应用 (Hydrogel type temporary adhesive and preparation method and application thereof ) 是由 曹大学 李玉博 于 2021-07-27 设计创作，主要内容包括：本发明属于粘合剂制备技术领域,具体涉及一种水凝胶型临时粘合剂及其制备方法和应用。该凝胶型临时粘合剂的原料包括聚酯丙烯酸酯、聚乙二醇类大分子和助剂,还包括丙烯酸异冰片酯或含酰胺基团类大分子。该水凝胶型临时粘合剂粘合基材后具有较好的剥离性能,且剥离后基材表面无残留的粘合剂,该粘合剂可以在光学镜头、手机摄像头、镜头镜片等基材加工过程中作为临时保护胶使用,将该粘合剂从基材表面脱落时无需加热,直接将基材浸泡后,粘合剂会自动脱落,不会影响基材的性能,基材表面也不会残留该粘合剂。(The invention belongs to the technical field of adhesive preparation, and particularly relates to a hydrogel type temporary adhesive as well as a preparation method and application thereof. The raw materials of the gel type temporary adhesive comprise polyester acrylate, polyethylene glycol macromolecules, an auxiliary agent, and isobornyl acrylate or amide group-containing macromolecules. The hydrogel type temporary adhesive has good stripping performance after being adhered to a substrate, and has no residual adhesive on the surface of the substrate after being stripped, the adhesive can be used as a temporary protective adhesive in the processing process of the substrates such as an optical lens, a mobile phone camera, a lens and the like, the adhesive is not required to be heated when falling off from the surface of the substrate, the substrate is directly soaked, the adhesive can automatically fall off, the performance of the substrate cannot be influenced, and the adhesive cannot be residual on the surface of the substrate.)

1. A hydrogel type temporary adhesive is characterized in that raw materials comprise a monomer mixture and an auxiliary agent; the monomer mixture comprises polyester acrylate and polyethylene glycol macromolecules;

the monomer mixture also comprises isobornyl acrylate or amide group-containing macromolecules;

the amide-containing macromolecule further has a radical polymerizable group.

2. The hydrogel-type temporary adhesive agent as claimed in claim 1, wherein when the monomer mixture comprises the amide group-containing macromolecules, the monomer mixture further comprises a monomer having a triazine ring structure;

the monomer containing the triazine ring structure has the following structural formula,

3. the hydrogel-type temporary binder according to claim 1 or 2, wherein the monomer mixture comprises 1 to 5 parts by weight of polyester acrylate, 1 to 5 parts by weight of polyethylene glycol-based macromolecule, and 1 to 5 parts by weight of isobornyl acrylate; or the like, or, alternatively,

the monomer mixture comprises 1-5 parts of polyester acrylate, 1-5 parts of polyethylene glycol macromolecules and 1-5 parts of amide group-containing macromolecules.

4. The hydrogel temporary binder of claim 3, wherein when the monomer mixture comprises the amide group-containing macromolecule, the monomer mixture further comprises 1 to 5 parts of a triazine ring structure-containing monomer.

5. The hydrogel temporary binder of any one of claims 1 to 4, wherein the polyester acrylate is an acrylate macromer containing double bonds and having a functionality of 1 to 6;

the polyethylene glycol macromolecule has the following structural formula,

wherein, the molecular weight of the polyethylene glycol macromolecule is 200-;

the amide-containing macromolecule can be at least one of methacrylamide, N-dimethylacrylamide, N-methylolacrylamide and polymethacrylamide.

6. The hydrogel temporary binder of any one of claims 1 to 5, wherein the raw materials of the hydrogel temporary binder further comprise 1 to 4 parts of starch; and/or the presence of a gas in the gas,

also comprises 1-5 parts of mercaptan;

the thiol has a thiol functionality of 2 to 4.

7. The hydrogel temporary binder of any one of claims 1 to 6, wherein the auxiliary agent comprises a photoinitiator and a silane coupling agent;

the amount of the photoinitiator is 1-10% of the total weight of the monomer mixture;

the dosage of the silane coupling agent is 1-5% by weight of the total weight of the monomer mixture.

8. A method for preparing a hydrogel-type temporary bonding agent as claimed in any one of claims 1 to 7, comprising the steps of,

under the irradiation of light, an auxiliary agent is added into the monomer mixture to obtain the hydrogel type temporary adhesive.

9. The method of claim 8, further comprising the step of adding a mercaptan and/or a starch after the addition of the adjuvant.

10. Use of a temporary binding agent of the hydrogel type according to any of claims 1 to 7 or of a temporary binding agent of the hydrogel type prepared by a process according to any of claims 8 to 9 for the processing of glass and/or lenses.

Technical Field

The invention belongs to the technical field of adhesive preparation, and particularly relates to a hydrogel type temporary adhesive as well as a preparation method and application thereof.

Background

Temporary bonding refers to the temporary bonding of an adherend for a specific purpose. With the rapid development of the industrial processing industry, more and more fields need to be temporarily fixed, such as multilayer glass processing, silicon wafer grinding and the like. In these areas, the basic performance requirements for adhesives are consistent, and there is a need for good adhesion and rapid adhesive failure. The related adhesives that have been reported are relatively messy, involving a number of different systems, such as polyurethanes, epoxies, acrylics, etc., but with varying end effects.

In the prior art, temporary bonding is performed in various ways, such as (1) thermal peeling is performed to deactivate the bonding of the adhesive by applying a certain amount of heat; (2) the gas-generating component or water-soluble substance is added to improve the later peeling property after temporary fixation. However, these two methods generally require high temperature at the time of peeling, require high temperature, limit the application thereof, and leave a part of the temporary pressure-sensitive adhesive on the surface of the adherend after peeling.

Chinese patent document CN107163882A discloses a heat-peelable temporary fixing adhesive which comprises an acrylic polymer, an isopropyl acrylamide microgel, a heat peeling factor, starch and an auxiliary agent, but the temporary fixing adhesive has a good peeling strength under a heating condition, and the peeling property of the temporary fixing adhesive is unstable and incomplete, and a small amount of the temporary fixing adhesive remains on an adherend.

Disclosure of Invention

Therefore, the technical problem to be solved by the present invention is to overcome the defects of the prior art that the temporary fixing adhesive remains and easily damages a substrate (adherend) after being peeled off and needs to be heated to realize the peeling effect, and the like, so as to provide a hydrogel type temporary adhesive, a preparation method and an application thereof.

Therefore, the invention provides the following technical scheme.

The invention provides a hydrogel type temporary adhesive, which comprises the following raw materials of a monomer mixture and an auxiliary agent; the monomer mixture comprises polyester acrylate and polyethylene glycol macromolecules;

the monomer mixture also comprises isobornyl acrylate or amide group-containing macromolecules;

the amide-containing macromolecule further has a radical polymerizable group.

When the monomer mixture comprises an amide group-containing macromolecule, the monomer mixture further comprises a triazine ring structure-containing monomer;

the monomer containing the triazine ring structure has the following structural formula,

further, the monomer mixture comprises 1-5 parts of polyester acrylate, 1-5 parts of polyethylene glycol macromolecules and 1-5 parts of isobornyl acrylate in parts by weight; or the like, or, alternatively,

the monomer mixture comprises 1-5 parts of polyester acrylate, 1-5 parts of polyethylene glycol macromolecules and 1-5 parts of amide group-containing macromolecules.

Further, when the monomer mixture includes the amide group-containing macromolecule, the monomer mixture further includes 1 to 5 parts of a triazine ring structure-containing monomer.

The polyester acrylate is an acrylate macromonomer containing double bonds and having a functionality of 1-6;

the polyethylene glycol macromolecule has the following structural formula,

wherein, the molecular weight of the polyethylene glycol macromolecule is 200-;

the amide-containing macromolecule can be at least one of methacrylamide, N-dimethylacrylamide, N-methylolacrylamide and polymethacrylamide.

The polyester acrylate may be a monomer having a functionality of 2 to 6 capable of radical polymerization, and is not particularly limited, and a monomer having the following structure is preferred in the present invention:

the polyethylene glycol macromolecule has the following structural formula,

wherein, the molecular weight of the polyethylene glycol macromolecule is 200-.

The raw materials of the hydrogel type temporary adhesive also comprise 1-4 parts of starch; and/or the presence of a gas in the gas,

also comprises 1-5 parts of mercaptan;

the thiol has a thiol functionality of 2 to 4.

The auxiliary agent comprises a photoinitiator and a silane coupling agent;

the amount of the photoinitiator is 1-10% of the total weight of the monomer mixture;

the dosage of the silane coupling agent is 1-5% by weight of the total weight of the monomer mixture.

The photoinitiator is at least one of alpha, alpha-dimethoxy-alpha-phenylacetophenone (651 for short), 1-hydroxycyclohexyl phenyl ketone (184 for short), phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (819 for short), diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide (TPO for short) and 2-isopropyl thioxanthone (ITX for short);

the silane coupling agent may be, but is not limited to, gamma-methacryloxypropyltrimethoxysilane.

The invention also provides a preparation method of the hydrogel type temporary adhesive, which comprises the following steps,

under the irradiation of light, an auxiliary agent is added into the monomer mixture to obtain the hydrogel type temporary adhesive.

Furthermore, the method also comprises the step of adding the mercaptan and/or the starch after the addition of the auxiliary agent.

The invention also provides an application of the hydrogel type temporary adhesive or the hydrogel type temporary adhesive prepared by the method in processing glass and/or lenses.

The hydrogel type temporary adhesive is applied to processing of glass and/or lenses, particularly, the adhesive can be used for fixing glass substrates, lenses of mobile phones (cameras) and the like in the processing process, and after cutting is finished, the adhesive is removed by soaking in water.

After the hydrogel type temporary adhesive is adhered to a base material, the adhesion effect is realized after UV curing, and then the base material with the cured adhesive is soaked in water to achieve the stripping effect.

The technical scheme of the invention has the following advantages:

1. the raw materials of the hydrogel type temporary adhesive provided by the invention comprise polyester acrylate, polyethylene glycol macromolecules, an auxiliary agent, and isobornyl acrylate or amide group-containing macromolecules. The hydrogel type temporary adhesive has good stripping performance after being adhered to a substrate, and has no residual adhesive on the surface of the substrate after being stripped, the adhesive can be used as a temporary protective adhesive in the processing process of the substrates such as an optical lens, a mobile phone camera, a lens and the like, the adhesive is not required to be heated when falling off from the surface of the substrate, the substrate is directly soaked, the adhesive can automatically fall off, the performance of the substrate cannot be influenced, and the adhesive cannot be residual on the surface of the substrate. The adhesive can form a three-dimensional skeleton structure, has better strength, mechanical property and cohesiveness, can well protect a base material from being influenced by a processing technology when used as a temporary protective adhesive, can fall off from the surface of the base material after the protective action is finished, and does not need to be heated and assisted by external force; on one hand, after the base material with the adhesive is soaked, a large number of hydrogen bonds are formed among molecules, and the hydrogel is locally coiled and can be spontaneously and rapidly peeled off from the surface of the base material; on the other hand, the adhesive also has good water absorption property, and the adhesive can be spontaneously peeled from the surface of a substrate by soaking the substrate with the adhesive in water and causing volume expansion after the adhesive absorbs water and combining the property that hydrogel is curled when encountering water. Isobornyl acrylate or amide group-containing macromolecules are used as raw materials to perform polymerization reaction with polyester acrylate and polyethylene glycol macromolecules to obtain the hydrogel type temporary adhesive.

2. The hydrogel type temporary adhesive provided by the invention is added with the triazine ring structure-containing monomer in the preparation process of the adhesive, and can form a stable and rigid regular hexagonal structure through intermolecular hydrogen bonds, so that the stripping effect of the adhesive on a substrate can be further improved.

By adding starch into the adhesive, the starch can be fixed in a three-dimensional framework, and the mechanical property of the adhesive is further enhanced. After the mercaptan is added, oxygen inhibition can be avoided, and the bonding performance of the adhesive is further improved due to thioether bonds generated by polymerization reaction.

According to the invention, the polyester acrylate and the polyethylene glycol macromolecular monomers are optimized, meanwhile, the polyester acrylate, the polyethylene glycol macromolecular and the isobornyl acrylate are adopted as the monomer mixture in specific dosage, or the polyester acrylate, the polyethylene glycol macromolecular, the amide group-containing macromolecular and the triazine ring structure-containing monomer are adopted in specific dosage, so that the obtained adhesive has more excellent stripping effect.

Detailed Description

The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.

The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.

Example 1

This example provides a method for preparing a hydrogel-type temporary bonding agent, which is performed under a yellow light lamp, comprising the steps of,

under a yellow light, 2.5kg of dipentaerythritol pentaacrylate, 2.5kg of ethylene glycol monomethyl ether acrylate and 1.5kg of isobornyl acrylate are mixed, 0.5kg of photoinitiator (651) is added, then the mixture is heated to 50 ℃, stirred until the photoinitiator is completely dissolved, then 5kg of mercaptan, 0.1kg of gamma-methacryloxypropyl trimethoxy silane, 0.2kg of fumed silica and 3kg of tapioca starch are added after the temperature is reduced to the room temperature, the mixture is stirred to be completely mixed at the room temperature, the fully mixed materials are put into a three-roll grinder to be ground until the particle size is less than 15 mu m, and the materials are discharged to obtain the adhesive which is stored in a dark place.

Example 2

This example provides a method for preparing a hydrogel-type temporary bonding agent, which is performed under a yellow light lamp, comprising the steps of,

under a yellow light, 3.0kg of dipentaerythritol pentaacrylate, 2.5kg of ethylene glycol monomethyl ether acrylate and 1.5kg of isobornyl acrylate are mixed, 0.6kg of photoinitiator (819) is added, then the mixture is heated to 50 ℃, stirred until the photoinitiator is completely dissolved, then 5kg of mercaptan, 0.1kg of gamma-methacryloxypropyl trimethoxy silane, 0.2kg of fumed silica and 3kg of corn starch are added after the temperature is reduced to room temperature, the mixture is stirred to be completely and uniformly mixed at the room temperature, the fully mixed materials are put into a three-roll grinder to be ground until the particle size is less than 15 mu m, and the materials are discharged to obtain the adhesive which is stored in a dark place.

Example 3

This example provides a method for preparing a hydrogel-type temporary bonding agent, which is performed under a yellow light lamp, comprising the steps of,

under a yellow light, 4.0kg of dipentaerythritol pentaacrylate, 2.5kg of ethylene glycol monomethyl ether acrylate and 1.5kg of isobornyl acrylate are mixed, 0.7kg of photoinitiator (651) is added, then the mixture is heated to 50 ℃, stirred until the photoinitiator is completely dissolved, then 5kg of mercaptan, 0.1kg of gamma-methacryloxypropyl trimethoxy silane, 0.2kg of fumed silica and 3kg of tapioca starch are added after the temperature is reduced to room temperature, the mixture is stirred to be completely mixed at the room temperature, the fully mixed materials are put into a three-roll grinder to be ground until the particle size is less than 15 mu m, and the materials are discharged to obtain the adhesive which is stored in a dark place.

Example 4

This example provides a method for preparing a hydrogel-type temporary bonding agent, which is performed under a yellow light lamp, comprising the steps of,

under a yellow light, 2.5kg of dipentaerythritol pentaacrylate, 2.5kg of ethylene glycol monomethyl ether acrylate and 1.5kg of isobornyl acrylate are mixed, 0.5kg of photoinitiator (651) is added, then the mixture is heated to 50 ℃, stirred until the photoinitiator is completely dissolved, then 4.0kg of mercaptan, 0.1kg of gamma-methacryloxypropyl trimethoxy silane, 0.2kg of fumed silica and 3kg of corn starch are added after the temperature is reduced to room temperature, the mixture is stirred at the room temperature until the mixture is completely mixed uniformly, the fully mixed materials are put into a three-roll grinder to be ground until the particle size is less than 15 mu m, and the materials are discharged to obtain the adhesive which is preserved in a dark place.

Example 5

This example provides a method for preparing a hydrogel-type temporary bonding agent, which is performed under a yellow light lamp, comprising the steps of,

under a yellow light, 1.0kg of dipentaerythritol pentaacrylate, 5.0kg of ethylene glycol monomethyl ether acrylate and 1.5kg of isobornyl acrylate are mixed, then 0.5kg of photoinitiator (651) is added, then the mixture is heated to 50 ℃, stirred until the photoinitiator is completely dissolved, then 3.0kg of mercaptan, 0.1kg of gamma-methacryloxypropyl trimethoxy silane, 0.2kg of fumed silica and 3kg of tapioca starch are added after the temperature is reduced to room temperature, the mixture is stirred at the room temperature until the mixture is completely mixed uniformly, the fully mixed materials are put into a three-roll grinder to be ground until the particle size is less than 15 mu m, and the materials are discharged to obtain the adhesive which is preserved in a dark place.

Example 6

This example provides a method for preparing a hydrogel-type temporary bonding agent, which is performed under a yellow light lamp, comprising the steps of,

under a yellow light, mixing 2.5kg of dipentaerythritol pentaacrylate, 2.5kg of ethylene glycol monomethyl ether acrylate and 2.5kg of N, N-dimethylacrylamide, then adding 0.4kg of photoinitiator (651), then heating to 50 ℃, stirring until the photoinitiator is completely dissolved, then cooling to room temperature, adding 3.0kg of mercaptan, 0.1kg of gamma-methacryloxypropyl trimethoxysilane, 0.2kg of fumed silica and 3.0kg of tapioca starch, stirring at room temperature until the mixture is completely and uniformly mixed, grinding the fully mixed materials in a three-roll grinder until the particle size is less than 15 mu m, discharging to obtain the adhesive, and storing in a dark place.

Example 7

This example provides a method for preparing a hydrogel-type temporary bonding agent, which is performed under a yellow light lamp, comprising the steps of,

under a yellow light, 1.0kg of dipentaerythritol pentaacrylate, 2.5kg of ethylene glycol methyl ether acrylate, 2.5kg of polymethacrylamide and 1.0kg of 2-vinyl-4, 6-diamino-1, 3, 5-triazine are mixed, 0.3kg of photoinitiator (TPO) is added, then the mixture is heated to 50 ℃, stirred until the photoinitiator is completely dissolved, then the mixture is cooled to room temperature, 3.0kg of mercaptan, 0.1kg of gamma-methacryloxypropyltrimethoxysilane, 0.2kg of fumed silica and 3.0kg of tapioca starch are added, the mixture is stirred to be completely and uniformly mixed at room temperature, the fully mixed materials are put into a three-roll grinder to be ground until the particle size is less than 15 mu m, and the materials are discharged to obtain the adhesive which is preserved in a dark place.

Comparative example 1

This comparative example provides a method for preparing a hydrogel type temporary bonding agent, which was performed under a yellow light lamp, comprising the steps of,

under a yellow light, 2.5kg of dipentaerythritol pentaacrylate and 2.5kg of ethylene glycol methyl ether acrylate are mixed, then 0.5kg of photoinitiator (651) is added, then the mixture is heated to 50 ℃, stirred until the photoinitiator is completely dissolved, then the mixture is cooled to room temperature, 5kg of mercaptan, 0.1kg of gamma-methacryloxypropyl trimethoxysilane, 0.2kg of fumed silica and 3kg of tapioca starch are added, the mixture is stirred to be completely and uniformly mixed at room temperature, the fully mixed materials are placed in a three-roll grinder to be ground until the particle size is less than 15 mu m, and the materials are discharged to obtain the adhesive which is stored in a dark place.

Test examples

The test example provides performance testing and test results for the adhesives of examples 1-7 and comparative example 1, the test results are shown in table 1, and the test methods are as follows:

the adhesives prepared in each example and comparative example were injected into a polytetrafluoroethylene cylinder having a diameter of 10mm and a height of 10mm, respectively, using 395/365nm LED lamp, 700 and 800mw/cm²Irradiating for 10s, after UV curing, measuring the thickness of the cured part by using a vernier caliper, namely the curing depth.

Hardness of the binder: the cured adhesive was tested using a shore a durometer.

Shear strength of adhesive: the bonding material is glass/glass, and the measuring method refers to the standard ISO 4587.

Test method for adhesive peeling: taking two pieces of glass of 1cm multiplied by 1cm as base materials, coating an adhesive on one piece of glass in a dispensing mode, then jointing the two pieces of glass with the other piece of glass, placing the jointed two pieces of glass in an 395/365nm LED lamp at 700 plus materials of 800mw/cm²Irradiating for 10s, after UV curing, placing the attached glass in a water bath at 25 ℃, ultrasonically processing, and observing the separation time of the two pieces of glass, wherein the test results of each example and each comparative example are shown in Table 1; wherein after curing, the thickness of the adhesive between the two panes is about 200 μm.

TABLE 1 Performance test results for the adhesives of the examples and comparative examples

From the results in table 1, it can be seen that the hydrogel type temporary adhesive provided by the present invention has a good peeling effect, a short peeling time, and no residue; in particular, when dipentaerythritol pentaacrylate, ethylene glycol methyl ether acrylate and N, N-dimethylacrylamide are used in specific amounts, the obtained hydrogel-type temporary adhesive is superior in adhesion effect, shorter in peeling time, and free from residue on the surface of the substrate.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.