CN114958300A - Bio-based pressure-sensitive adhesive and preparation method thereof - Google Patents
Bio-based pressure-sensitive adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN114958300A CN114958300A CN202210658487.7A CN202210658487A CN114958300A CN 114958300 A CN114958300 A CN 114958300A CN 202210658487 A CN202210658487 A CN 202210658487A CN 114958300 A CN114958300 A CN 114958300A
- Authority
- CN
- China
- Prior art keywords
- sensitive adhesive
- bio
- based pressure
- preparation
- epoxidized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J191/00—Adhesives based on oils, fats or waxes; Adhesives based on derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
Abstract
The invention belongs to the technical field of pressure-sensitive adhesives, and particularly relates to a bio-based pressure-sensitive adhesive and a preparation method thereof. The preparation method of the bio-based pressure-sensitive adhesive comprises the following steps: 1) mixing epoxy vegetable oil and ethyl acetate, adding rosin ester and an antioxidant, and oscillating and dissolving to obtain a mixed solution; 2) cooling the mixed solution to-5 ℃, keeping the temperature for 15-25 min, then adding phosphoric acid, and carrying out oscillation, heating and ultrasonic reaction to obtain a reaction solution; 3) and coating the reaction solution on a base material, curing for 10-30 min at 22-28 ℃, and then carrying out constant temperature and humidity regulation to obtain the material. Compared with the bio-based pressure-sensitive adhesive in the prior art, the pressure-sensitive adhesive prepared by the method has the advantages that the peel strength, the initial adhesion and the aging resistance are greatly improved, so that technical support can be provided for the development and application of a novel bio-based pressure-sensitive adhesive material.
Description
Technical Field
The invention belongs to the technical field of pressure-sensitive adhesives, and particularly relates to a bio-based pressure-sensitive adhesive and a preparation method thereof.
Background
Pressure-sensitive adhesives, i.e., pressure-sensitive adhesives (PSAs), are adhesives that require only a small amount of external force to adhere to a variety of substrates. The pressure-sensitive adhesive elastomer usually has both the viscous characteristic of liquid and the elastic characteristic of solid, when the pressure-sensitive adhesive spreads on the rough surface of the base material, the contact area of the adhesive and an adherend can be increased due to the wettability and plasticity of the pressure-sensitive adhesive, so that firm adhesion is formed, and the pressure-sensitive adhesive elastomer has the characteristics of easiness in adhering and easiness in removing. In view of the excellent characteristics of pressure-sensitive adhesives, the global pressure-sensitive adhesive market has been rapidly growing in recent years, and the asia-pacific region is the largest and fastest growing market in the global pressure-sensitive adhesive market, and the pressure-sensitive adhesives are widely applied to a plurality of fields such as automobiles, foods, packaging, electrical and electronic fields, medical fields and the like.
In commercial production, it is required that the pressure-sensitive adhesive is not subjected to interfacial failure, nor to cohesive failure and mixing failure. The interface failure means that in a stripping experiment, the pressure-sensitive adhesive has high bonding strength and insufficient bonding strength with the surface of the base material, so that the colloid is completely separated from the surface of the base material, and the surface of the base material has no residual adhesive basically; cohesive failure means that the cohesive force of the pressure-sensitive adhesive is small, so that the inside of the adhesive layer is damaged, and partial residual adhesive is left on the surface of the base material; mixed failure is a phenomenon combining two failure modes, interfacial failure and cohesive failure.
Currently, pressure sensitive adhesives are mainly derived from petrochemicals, in addition to traditional natural rubber, resins. However, due to the increasing shortage and non-regeneration of petroleum resources, new materials which are sustainable are promising from the aspect of development strategy. Compared with the traditional petroleum-based pressure-sensitive adhesive, the bio-based pressure-sensitive adhesive can reduce the using amount of petroleum and the discharge amount of wastewater in the production process, thereby protecting the environment, saving the cost and improving the economic benefit, so the bio-based pressure-sensitive adhesive is concerned by students.
At present, the research on the vegetable oil as the matrix in the research on the bio-based pressure-sensitive adhesive is the most extensive, and the preparation of the pressure-sensitive adhesive is mainly carried out by the ring-opening crosslinking copolymerization after the unsaturated double bond in the vegetable oil is epoxidized under the action of a catalyst. However, in the production process and the actual use process of the existing vegetable oil pressure-sensitive adhesive, the phenomena of insufficient adhesive strength of the pressure-sensitive adhesive and aging caused by the influence of light, heat, oxygen and other environmental factors are easy to occur, and the higher use requirement of the pressure-sensitive adhesive product cannot be met.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a method for preparing a bio-based pressure-sensitive adhesive, which has a simple process and can effectively improve initial adhesion, peel strength and aging resistance of the bio-based pressure-sensitive adhesive.
The invention also aims to provide a bio-based pressure-sensitive adhesive which has excellent initial adhesion, peeling strength and ageing resistance.
In order to realize the purpose, the preparation method of the bio-based pressure-sensitive adhesive adopts the technical scheme that:
a preparation method of a bio-based pressure-sensitive adhesive comprises the following steps:
1) mixing epoxy vegetable oil and ethyl acetate, adding rosin ester and an antioxidant, and oscillating and dissolving to obtain a mixed solution;
2) cooling the mixed solution to-5 ℃, keeping the temperature for 15-25 min, then adding phosphoric acid, and carrying out oscillation, heating and ultrasonic reaction to obtain a reaction solution;
3) coating the reaction solution on a substrate, curing for 10-30 min at 22-28 ℃, and then carrying out constant temperature and humidity regulation to obtain the material;
wherein, per gram of epoxy vegetable oil, the dosage of the corresponding ethyl acetate is 0.8-1.2 mL, and the dosage of the corresponding phosphoric acid is 0.051-0.0595 g; the mass ratio of the epoxy vegetable oil to the rosin ester to the antioxidant is 1 to (0.65-0.75) to (0.006-0.009); the antioxidant is one of caffeic acid, di-tert-butyl-p-cresol, tert-butyl hydroxy anisole, propyl gallate and tea polyphenol palmitate.
When the bio-based pressure-sensitive adhesive is prepared, the crosslinking copolymerization is carried out by utilizing partial phenolic hydroxyl and/or carboxyl of a plurality of specific antioxidants, epoxy groups of epoxy vegetable oil and phosphoric acid through esterification and etherification, so that the cohesive strength of the pressure-sensitive adhesive is enhanced; meanwhile, the unreacted phenolic hydroxyl and/or carboxyl polar functional groups enhance the wettability of the pressure-sensitive adhesive. The aging resistance of the unreacted phenolic hydroxyl group on the antioxidant and the ultraviolet absorption capability of the benzene ring in the pressure-sensitive adhesive greatly delay the aging problem of the pressure-sensitive adhesive in indoor and outdoor environmental use.
The preparation method of the bio-based pressure-sensitive adhesive has the advantages of simple and easily obtained raw materials and low process operation difficulty, and particularly, performance test tests show that the pressure-sensitive adhesive prepared by the method has no interface damage and cohesive damage, the 180-degree peel strength is 0.967-2.460N/cm, the annular initial adhesion is 0.97-3.10N, and the 180-degree peel strength residual rate after aging is 157-366%. The invention can well balance the crosslinking degree and the wettability of the pressure-sensitive adhesive, and greatly improves the peel strength, the initial adhesion and the ageing resistance compared with the bio-based pressure-sensitive adhesive in the prior art.
In the invention, the epoxy vegetable oil is not specially limited, and only the epoxy vegetable oil with relatively high unsaturation degree is adopted to ensure the performance of the bio-based pressure-sensitive adhesive. Preferably, in the step 1), the epoxidized vegetable oil is one of epoxidized soybean oil, epoxidized sunflower oil, epoxidized rapeseed oil, epoxidized Canola oil, epoxidized castor oil and epoxidized linseed oil; more preferably, the epoxidized vegetable oil is epoxidized soybean oil, and the epoxy value of the epoxidized soybean oil is 6.1-6.5%.
The purpose of the heating ultrasound is to promote mass and heat transfer between the reaction substance and the phosphoric acid in the reaction system and accelerate the reaction. Preferably, in the step 2), the temperature of the heating ultrasonic reaction is 48-52 ℃.
Based on the purposes of promoting the conversion of raw materials, balancing the crosslinking degree and wettability of the polymer and improving the performance of the pressure-sensitive adhesive, preferably, in the step 2), the oscillating and heating ultrasonic reaction is specifically as follows: performing vortex oscillation for 25-35 s, heating and ultrasonic treatment for 25-35 s, and circulating for 5-6 times; more preferably, the vortex oscillation is carried out for 30s, the heating and ultrasonic treatment are carried out for 30s, and the circulation is carried out for 5-6 times.
The invention does not specially limit the type of the base material used for coating, and the adopted base material only needs to meet the coating requirement. Preferably, in step 3), the substrate is one of PET, PI, PVC, non-woven fabric, aluminum foil, copper foil, and PET aluminum-plated film. More preferably a PET substrate.
Preferably, in step 3), the constant temperature and humidity are adjusted as follows: adjusting for 20-28 h in a constant temperature and humidity box with the temperature of 22-24 ℃ and the humidity of 45-55%; more preferably, the temperature and humidity are adjusted in a constant temperature and humidity box with the temperature of 23 ℃ and the humidity of 50 percent for 24 hours.
The invention relates to a bio-based pressure-sensitive adhesive, which adopts the technical scheme that:
a bio-based pressure-sensitive adhesive is prepared by the method.
Compared with the traditional petroleum-based pressure-sensitive adhesive, the bio-based pressure-sensitive adhesive is more environment-friendly, and performance test experiments of the pressure-sensitive adhesive show that the 180-degree peel strength of the pressure-sensitive adhesive is 0.967-2.460N/cm, the annular initial adhesion is 0.97-3.10N, and the 180-degree peel strength residual rate after aging is 157-366%, which is far superior to that of the existing bio-based pressure-sensitive adhesive material, so that technical support can be provided for development and application of novel bio-based pressure-sensitive adhesive materials.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited thereto. The equipment and reagents used in the examples and the experimental examples were commercially available except as specifically indicated. Wherein: in the following examples and test examples, the following test devices were used: normal temperature adhesive tape holding power tester (HTS-BCL 2220): guangdong department of general extract instruments ltd; full-function material tester (LT-1000): shannsi test instruments ltd; coater (1806F/100): guangzhou City Shenghua practice Co., Ltd; vortex oscillator (XW-80A): lonbel instruments manufacturing, Inc., of Haiman; ultrasonic cleaner (KQ-300B): kunshan ultrasonic instruments Inc.
The invention provides a preparation method of a bio-based pressure-sensitive adhesive, which comprises the following steps:
1) mixing epoxy vegetable oil and ethyl acetate, adding rosin ester and an antioxidant, and oscillating and dissolving to obtain a mixed solution;
2) cooling the mixed solution to-5 ℃, keeping the temperature for 15-25 min, then adding phosphoric acid, and carrying out oscillation, heating and ultrasonic reaction to obtain a reaction solution;
3) coating the reaction solution on a substrate, curing for 10-30 min at 22-28 ℃, and then carrying out constant temperature and humidity regulation to obtain the material;
in the step 1), the dosage of ethyl acetate per gram of epoxy vegetable oil is 0.8-1.2 mL, more preferably 1 mL. The mass ratio of the epoxy vegetable oil to the rosin ester to the antioxidant is 1 to (0.65-0.75) to (0.006-0.009); more preferably, the mass ratio of the epoxy vegetable oil to the rosin ester to the antioxidant is 1: 0.7: 0.006-0.009. The antioxidant is one of caffeic acid, di-tert-butyl-p-cresol, tert-butyl hydroxy anisole, propyl gallate and tea polyphenol palmitate.
In the invention, the selection of the epoxy vegetable oil is not specially limited, and only the epoxy vegetable oil with higher unsaturation degree is adopted to ensure the performance of the bio-based pressure-sensitive adhesive. Preferably, in the step 1), the epoxidized vegetable oil is one of epoxidized soybean oil, epoxidized sunflower oil, epoxidized rapeseed oil, epoxidized Canola oil, epoxidized castor oil and epoxidized linseed oil; more preferably, the epoxidized vegetable oil is epoxidized soybean oil, and the epoxy value of the epoxidized soybean oil is 6.1-6.5%. In the following examples of the present invention, epoxidized soybean oil, available from Mecline, having an epoxy value of 6.12%, was specifically used.
In the invention, in the step 2), phosphoric acid is both a catalyst and a reaction raw material, the adding amount of phosphoric acid can be determined according to the reaction effect between phosphoric acid and the epoxy vegetable oil and the antioxidant, and preferably, the dosage of phosphoric acid is 0.051-0.0595 g per gram of epoxy vegetable oil. In the following examples, the phosphoric acid is commercially available phosphoric acid with a concentration of 85%, and the amount of the phosphoric acid added per gram of the epoxy vegetable oil is 0.06 to 0.07g, and more preferably 0.07g, corresponding to 85%.
In the step 2), the mixed solution is directly reacted with phosphoric acid, and the reaction effect is severely affected due to the fact that epoxy bonds of the epoxy vegetable oil are active, so that the temperature needs to be reduced in advance to reduce the reaction speed after the phosphoric acid is added. Preferably, in the invention, the mixed solution is cooled to-5 to 5 ℃ and kept for 15 to 25min, and then phosphoric acid is added for reaction, more preferably: cooling the mixed solution to 0 ℃, keeping the temperature for 20min, and adding phosphoric acid for reaction.
The purpose of the heating ultrasound is to promote mass and heat transfer between a reaction substance and a catalyst in a reaction system and accelerate the reaction. Preferably, in the step 2), the temperature of the heating ultrasonic reaction is 48-52 ℃, and more preferably 50 ℃.
Based on the purposes of promoting the conversion of raw materials, balancing the crosslinking degree and the wettability of the polymer and improving the performance of the pressure-sensitive adhesive, preferably, in the step 2), the oscillating and heating ultrasonic reaction is specifically: performing vortex oscillation for 25-35 s, heating and ultrasonic treatment for 25-35 s, and circulating for 5-6 times; more preferably, the vortex oscillation is carried out for 30s, the heating and ultrasonic treatment are carried out for 30s, and the circulation is carried out for 5-6 times.
The invention does not specially limit the type of the base material used for coating, and the adopted base material only needs to meet the coating requirement. Preferably, in step 3), the substrate is one of PET, PI, PVC, non-woven fabric, aluminum foil, copper foil, and PET aluminum-plated film. More preferably a PET substrate.
Preferably, in step 3), the constant temperature and humidity are adjusted as follows: and (3) adjusting for 20-28 h in a constant temperature and humidity box with the temperature of 22-24 ℃ and the humidity of 50%, and more preferably adjusting for 24h in a constant temperature and humidity box with the temperature of 23 ℃ and the humidity of 50%.
First, an embodiment
Example 1
The preparation method of the bio-based pressure-sensitive adhesive of the embodiment adopts the following steps:
1) 10g of epoxidized soybean oil (epoxy value is 6.12%, the same applies below) is put into a 50mL centrifuge tube, 10mL of ethyl acetate is added, then 7g of rosin ester and 0.09g of caffeic acid are accurately added, and vortex oscillation is carried out to dissolve the materials to obtain a mixed solution;
2) cooling the mixed solution to 0 ℃, keeping the temperature for 20min, then adding 0.7g of 85% phosphoric acid, carrying out vortex oscillation for 30s, carrying out heating and ultrasonic treatment at 50 ℃ for 30s, and repeating the operation for 5 times to obtain a reaction solution;
3) and (3) coating the reaction liquid through a coater, curing for 20min at 25 ℃, and adjusting for 24h in a constant temperature and humidity box with the temperature of 23 ℃ and the humidity of 50% to obtain the bio-based pressure-sensitive adhesive.
The bio-based pressure-sensitive adhesive of the embodiment is prepared by the preparation method.
Example 2
The preparation method of the bio-based pressure-sensitive adhesive of the embodiment adopts the following steps:
1) 10g of epoxidized soybean oil is put into a 50mL centrifuge tube, 10mL of ethyl acetate is added, then 7g of rosin ester and 0.09g of di-tert-butyl-p-cresol (BHT) are accurately added, and vortex oscillation is carried out to dissolve the epoxy soybean oil to obtain mixed solution;
2) cooling the mixed solution to 0 ℃, keeping the temperature for 20min, then adding 0.7g of 85% phosphoric acid, carrying out vortex oscillation for 30s, carrying out heating and ultrasonic treatment at 50 ℃ for 30s, and repeating the operation for 5 times to obtain a reaction solution;
3) and (3) coating the reaction liquid through a coater, curing for 20min at 25 ℃, and adjusting for 24h in a constant temperature and humidity box with the temperature of 23 ℃ and the humidity of 50% to obtain the bio-based pressure-sensitive adhesive.
The bio-based pressure-sensitive adhesive of the embodiment is prepared by the preparation method.
Example 3
The preparation method of the bio-based pressure-sensitive adhesive of the embodiment adopts the following steps:
1) 10g of epoxidized soybean oil is put into a 50mL centrifuge tube, 10mL of ethyl acetate is added, 7g of rosin ester and 0.09g of tert-Butyl Hydroxyanisole (BHA) are accurately added, and vortex oscillation is carried out to dissolve the epoxy soybean oil to obtain a mixed solution;
2) cooling the mixed solution to 0 ℃, keeping the temperature for 20min, then adding 0.7g of 85% phosphoric acid, carrying out vortex oscillation for 30s, carrying out heating and ultrasonic treatment at 50 ℃ for 30s, and repeating the operation for 6 times to obtain a reaction solution;
3) and (3) coating the reaction liquid through a coater, curing for 20min at 25 ℃, and adjusting for 24h in a constant temperature and humidity box with the temperature of 23 ℃ and the humidity of 50% to obtain the bio-based pressure-sensitive adhesive.
The bio-based pressure-sensitive adhesive of the embodiment is prepared by the preparation method.
Example 4
The preparation method of the bio-based pressure-sensitive adhesive of the embodiment adopts the following steps:
1) 10g of epoxidized soybean oil is put into a 50mL centrifuge tube, 10mL of ethyl acetate is added, then 7g of rosin ester and 0.09g of propyl gallate are accurately added, and vortex oscillation is carried out to dissolve the epoxy soybean oil to obtain a mixed solution;
2) cooling the mixed solution to 0 ℃, keeping the temperature for 20min, then adding 0.7g of 85% phosphoric acid, carrying out vortex oscillation for 30s, carrying out heating and ultrasonic treatment at 50 ℃ for 30s, and repeating the operation for 5 times to obtain a reaction solution;
3) and (3) coating the reaction liquid through a coater, curing for 20min at 25 ℃, and adjusting for 24h in a constant temperature and humidity box with the temperature of 23 ℃ and the humidity of 50% to obtain the bio-based pressure-sensitive adhesive.
The bio-based pressure-sensitive adhesive of the embodiment is prepared by the preparation method.
Example 5
The preparation method of the bio-based pressure-sensitive adhesive of the embodiment adopts the following steps:
1) 10g of epoxidized soybean oil is put into a 50mL centrifuge tube, 10mL of ethyl acetate is added, then 7g of rosin ester and 0.09g of tea polyphenol palmitate are accurately added, and vortex oscillation is carried out to dissolve the epoxy soybean oil and the tea polyphenol palmitate to obtain a mixed solution;
2) cooling the mixed solution to 0 ℃, keeping the temperature for 20min, then adding 0.7g of 85% phosphoric acid, carrying out vortex oscillation for 30s, carrying out heating and ultrasonic treatment at 50 ℃ for 30s, and repeating the operation for 5 times to obtain a reaction solution;
3) and (3) coating the reaction liquid through a coater, curing for 20min at 25 ℃, and adjusting for 24h in a constant temperature and humidity box with the temperature of 23 ℃ and the humidity of 50% to obtain the bio-based pressure-sensitive adhesive.
The bio-based pressure-sensitive adhesive of the embodiment is prepared by the preparation method.
Example 6
The preparation method of the bio-based pressure-sensitive adhesive of the embodiment adopts the following steps:
1) 10g of epoxidized soybean oil is taken out and put into a 50mL centrifuge tube, 10mL of ethyl acetate is added, 7g of rosin ester and 0.06g of caffeic acid are accurately added, and vortex oscillation is carried out to dissolve the epoxidized soybean oil to obtain a mixed solution;
2) cooling the mixed solution to 0 ℃, keeping the temperature for 20min, then adding 0.7g of 85% phosphoric acid, carrying out vortex oscillation for 30s, carrying out heating and ultrasonic treatment at 50 ℃ for 30s, and repeating the operation for 6 times to obtain a reaction solution;
3) and (3) coating the reaction liquid through a coater, curing for 20min at 25 ℃, and adjusting for 24h in a constant temperature and humidity box with the temperature of 23 ℃ and the humidity of 50% to obtain the bio-based pressure-sensitive adhesive.
The bio-based pressure-sensitive adhesive of the embodiment is prepared by the preparation method.
Second, comparative example
Comparative example 1
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 1, except that: the antioxidant caffeic acid was not added.
Comparative example 2
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 6, except that: the antioxidant caffeic acid was not added.
Comparative example 3
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 1, except that: 0.09g of ferulic acid was used instead of 0.09g of caffeic acid in example 1.
Comparative example 4
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 2, except that: 0.09g of t-butyl hydroquinone (TBHQ) was used in place of 0.09g of di-t-butyl-p-cresol (BHT) in example 2.
Comparative example 5
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 4, except that: 0.09g of gallic acid was used instead of 0.09g of propyl gallate in example 4.
Comparative example 6
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: 0.09g of tea polyphenol palmitate as described in example 5 was replaced by 0.09g of tea polyphenol.
Comparative example 7
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: 0.09g of beta-carotene was used instead of 0.09g of tea polyphenol palmitate as in example 5.
Comparative example 8
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: the dosage of the tea polyphenol palmitate is reduced from 0.09g to 0.03 g.
Comparative example 9
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: the dosage of the tea polyphenol palmitate is reduced from 0.09g to 0.06 g.
Comparative example 10
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: the dosage of the tea polyphenol palmitate is increased from 0.09g to 0.12 g.
Comparative example 11
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: the dosage of the tea polyphenol palmitate is increased from 0.09g to 0.15 g.
Comparative example 12
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: the amount of 85% phosphoric acid used was reduced from 0.7g to 0.6 g.
Comparative example 13
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: the amount of 85% phosphoric acid used was reduced from 0.7g to 0.65 g.
Comparative example 14
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: the amount of 85% phosphoric acid was increased from 0.7g to 0.75 g.
Comparative example 15
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: the amount of 85% phosphoric acid was increased from 0.7g to 0.8 g.
Comparative example 16
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: the amount of rosin ester is reduced from 7g to 6 g.
Comparative example 17
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: the amount of rosin ester was reduced from 7g to 6.5 g.
Comparative example 18
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: the dosage of the rosin ester is increased from 7g to 7.5 g.
Comparative example 19
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: the dosage of the rosin ester is increased from 7g to 8 g.
Comparative example 20
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: vortex was oscillated for 30s, and heat sonication was carried out at 50 ℃ for 30s, and the number of repetitions was reduced from 5 to 3.
Comparative example 21
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: vortex was oscillated for 30s, and heat sonication was carried out at 50 ℃ for 30s, and the number of repetitions was reduced from 5 to 4.
Comparative example 22
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: vortex was oscillated for 30s, and heat sonication was carried out at 50 ℃ for 30s, and this operation was repeated from 5 times to 6 times.
Comparative example 23
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: vortex was oscillated for 30s, and heat sonication was carried out at 50 ℃ for 30s, and this operation was repeated from 5 times to 7 times.
Comparative example 24
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: the ultrasonic heating temperature is reduced from 50 ℃ to 40 ℃.
Comparative example 25
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: the ultrasonic heating temperature is reduced from 50 ℃ to 45 ℃.
Comparative example 26
The preparation method of the bio-based pressure-sensitive adhesive of the comparative example is basically the same as that of example 5, except that: the ultrasonic heating temperature is increased from 50 ℃ to 55 ℃.
Third, test example
In the test example, the 180-degree peel strength, initial adhesion and aging resistance of the bio-based pressure-sensitive adhesive prepared in the examples 1 to 6 and the comparative examples 1 to 26 are respectively measured. The specific test process is as follows: the reaction solution obtained in step 2) of examples 1 to 6 and comparative examples 1 to 26 was coated on a PET film by an applicator, the coating thickness was 80 μm, the film was cured at room temperature for 20min, and the film was put into a constant temperature and humidity chamber at 23 ℃ and 50% humidity and conditioned for 24h, and then the peel strength at 180 degrees, the initial adhesion and the aging resistance were measured. The test method comprises the following steps: the 180 ° peel strength of the pressure sensitive adhesive was determined according to method a in ASTM D3330/D3330M-04 (2018). The initial tack of the pressure-sensitive adhesive is determined according to method A in ASTM D6195-03 (2019). The aging test of the pressure-sensitive adhesive is a reinforced destructive aging test (aging temperature is 60 ℃, relative humidity is 50%, aging time is 4 days), and is carried out according to ASTM D3611-06 (2019). The formula for calculating the 180 ° peel strength residual rate after aging refers to the prior art and is specifically shown below.
·
TABLE 1 examples and comparative examples 180 DEG Peel Strength before aging, Loop tack and 180 DEG Peel Strength Retention after aging
As can be seen from Table 1, in examples 1 to 6 provided by the invention, the 180 DEG peel strength is 0.967 to 2.460N/cm, the annular initial adhesion is 0.97 to 3.10N, the 180 DEG peel strength residual rate after aging is 157 to 366%, and the comprehensive performance is superior to that of comparative examples 1 to 26.
Among them, as is clear from the comparison results between comparative example 1 and examples 1 to 6 of the present invention, in the present invention, when a specific type of antioxidant (caffeic acid, di-tert-butyl-p-cresol, tert-butyl hydroxyanisole, propyl gallate, tea polyphenol palmitate) is applied to the synthesis reaction of the pressure-sensitive adhesive, the anti-aging performance of the pressure-sensitive adhesive can be significantly improved, and the 180 ° peel strength and the initial tack strength of the pressure-sensitive adhesive can be improved by 2.4 to 6.0 times and 2.3 to 7.2 times, respectively. Therefore, the specific antioxidant is added, so that the peel strength, initial adhesion and ageing resistance of the pressure-sensitive adhesive can be greatly and synergistically improved.
Further, it is known from the comparison results of the comparative examples 3 to 7 and the embodiment of the present invention that if the antioxidant is improperly used, the antioxidant has poor peel strength and initial adhesion, or poor aging resistance, cohesive failure occurs even in the epoxidized soybean oil pressure-sensitive adhesive with ferulic acid or gallic acid (comparative examples 3 and 5), interfacial failure occurs even in the epoxidized soybean oil pressure-sensitive adhesive with beta-carotene added (comparative example 7), and the use requirements of the pressure-sensitive adhesive cannot be met at all.
From the performance test results of example 5 and comparative examples 8-26, it can be seen that the performances of the pressure-sensitive adhesive are negatively affected to different degrees by changing the addition amount of the tea polyphenol palmitate (comparative examples 8-11), the phosphoric acid (comparative examples 12-15), the usage amount of the rosin ester (comparative examples 16-19) or the number of heating and ultrasonic cycles or the temperature (comparative examples 20-26). The pressure-sensitive adhesive of part of the comparison group has interfacial failure or cohesive failure phenomenon, and can not meet the use requirement.
In conclusion, the preparation method of the bio-based pressure-sensitive adhesive can prepare the bio-based pressure-sensitive adhesive with excellent peel strength, initial adhesion and aging resistance, shows good pressure-sensitive adhesive development and application potential, and provides a brand new thought for preparation and industrial application of novel bio-based pressure-sensitive adhesives.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The preparation method of the bio-based pressure-sensitive adhesive is characterized by comprising the following steps of:
1) mixing epoxy vegetable oil with ethyl acetate, adding rosin ester and an antioxidant, and shaking to dissolve to obtain a mixed solution;
2) cooling the mixed solution to-5 ℃, keeping the temperature for 15-25 min, then adding phosphoric acid, and carrying out oscillation, heating and ultrasonic reaction to obtain a reaction solution;
3) coating the reaction solution on a substrate, curing for 10-30 min at 22-28 ℃, and then carrying out constant temperature and humidity regulation to obtain the material;
wherein, per gram of epoxy vegetable oil, the dosage of the corresponding ethyl acetate is 0.8-1.2 mL, and the dosage of the corresponding phosphoric acid is 0.051-0.0595 g; the mass ratio of the epoxy vegetable oil to the rosin ester to the antioxidant is 1 to (0.65-0.75) to (0.006-0.009); the antioxidant is one of caffeic acid, di-tert-butyl-p-cresol, tert-butyl hydroxy anisole, propyl gallate and tea polyphenol palmitate.
2. The method of claim 1, wherein in step 1), the epoxidized vegetable oil is one of epoxidized soybean oil, epoxidized sunflower oil, epoxidized rapeseed oil, epoxidized Canola oil, epoxidized castor oil, and epoxidized linseed oil.
3. The preparation method of the bio-based pressure-sensitive adhesive according to claim 2, wherein in the step 1), the epoxidized vegetable oil is epoxidized soybean oil, and the epoxy value of the epoxidized soybean oil is 6.1-6.5%.
4. The preparation method of the bio-based pressure-sensitive adhesive according to claim 1, wherein in the step 2), the temperature of the heating ultrasonic reaction is 48-52 ℃.
5. The preparation method of the bio-based pressure-sensitive adhesive according to claim 1, wherein in the step 2), the specific process of the oscillation and heating ultrasonic reaction is as follows: vortex oscillation is carried out for 25-35 s, heating and ultrasonic treatment are carried out for 25-35 s, and circulation is carried out for 5-6 times.
6. The preparation method of bio-based pressure-sensitive adhesive according to claim 5, wherein in the step 2), the specific process of the oscillation and heating ultrasonic reaction is as follows: vortex and vibrate for 30s, heat and ultrasonically for 30s, and circulate for 5-6 times.
7. The method for preparing the bio-based pressure-sensitive adhesive according to claim 1, wherein in the step 3), the substrate is one of PET, PI, PVC, non-woven fabric, aluminum foil, copper foil and PET aluminized film.
8. The preparation method of the bio-based pressure-sensitive adhesive according to claim 1, wherein in the step 3), the constant temperature and humidity are adjusted as follows: and (3) adjusting for 20-28 h in a constant temperature and humidity box with the temperature of 22-24 ℃ and the humidity of 45-55%.
9. A bio-based pressure-sensitive adhesive, which is characterized by being prepared by the preparation method of the bio-based pressure-sensitive adhesive according to any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210658487.7A CN114958300B (en) | 2022-06-11 | 2022-06-11 | Bio-based pressure-sensitive adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210658487.7A CN114958300B (en) | 2022-06-11 | 2022-06-11 | Bio-based pressure-sensitive adhesive and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114958300A true CN114958300A (en) | 2022-08-30 |
| CN114958300B CN114958300B (en) | 2023-09-01 |
Family
ID=82961198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210658487.7A Active CN114958300B (en) | 2022-06-11 | 2022-06-11 | Bio-based pressure-sensitive adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114958300B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120059087A1 (en) * | 2010-08-18 | 2012-03-08 | Koch Carol A | Pressure sensitive adhesives based on renewable resources and related methods |
| US20130330549A1 (en) * | 2011-01-20 | 2013-12-12 | Kansas State University Research Foundation | Pressure sensitive adhesives, coatings, and films from plant oils |
| CN104968742A (en) * | 2012-12-05 | 2015-10-07 | 艾利丹尼森公司 | Pressure sensitive adhesives prepared from maleated vegetable oils and expoxidized vegetable oils |
| US20170009103A1 (en) * | 2014-01-24 | 2017-01-12 | Oregon State University | Pressure-sensitive adhesives based on carboxylic acids and epoxides |
| CN113316624A (en) * | 2018-11-20 | 2021-08-27 | 俄勒冈州立大学 | Ultraviolet radiation cured pressure sensitive adhesives from vegetable oils or animal fats |
-
2022
- 2022-06-11 CN CN202210658487.7A patent/CN114958300B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120059087A1 (en) * | 2010-08-18 | 2012-03-08 | Koch Carol A | Pressure sensitive adhesives based on renewable resources and related methods |
| US20130330549A1 (en) * | 2011-01-20 | 2013-12-12 | Kansas State University Research Foundation | Pressure sensitive adhesives, coatings, and films from plant oils |
| CN104968742A (en) * | 2012-12-05 | 2015-10-07 | 艾利丹尼森公司 | Pressure sensitive adhesives prepared from maleated vegetable oils and expoxidized vegetable oils |
| US20170009103A1 (en) * | 2014-01-24 | 2017-01-12 | Oregon State University | Pressure-sensitive adhesives based on carboxylic acids and epoxides |
| CN113316624A (en) * | 2018-11-20 | 2021-08-27 | 俄勒冈州立大学 | Ultraviolet radiation cured pressure sensitive adhesives from vegetable oils or animal fats |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114958300B (en) | 2023-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105219317B (en) | A kind of glutinous agent of the medical polyacrylate pressure-sensitive adhesive of environmental protection | |
| JP5789293B2 (en) | Adhesive composition for touch panel, adhesive film and touch panel | |
| CN106554728A (en) | Pressure-sensitive Protection glue band of a kind of butyl rubber base and preparation method thereof | |
| JP5522433B2 (en) | Adhesive, adhesive film and laminate obtained using the same | |
| TW201221605A (en) | Pressure-sensitive adhesive composition for touch panel, pressure-sensitive adhesive film and touch panel | |
| TW201249899A (en) | A method for increasing the bond strength of a pressure-sensitive adhesive layer comprising an upper and a lower surface | |
| KR101789557B1 (en) | Dual crosslinked tackified pressure sensitive adhesive | |
| AU2012347925A1 (en) | Vegetable oil-based pressure-sensitive adhesives | |
| CN107974221A (en) | A kind of multiple response attachment of polymers glue material and its application | |
| CN108314773A (en) | A kind of low viscosity, super branched polyurethane acrylic resin and its preparation method and application | |
| CN103871544B (en) | Anisotropic conductive film, for the compositions of this film and semiconductor device | |
| JP5086967B2 (en) | Adhesive resin composition and film using the adhesive resin composition | |
| CN112646517A (en) | Pressure-sensitive adhesive, pressure-sensitive adhesive tape, and preparation method and application thereof | |
| CN107987737A (en) | A kind of UV pressure-sensitive adhesives mixture and its preparation method and application | |
| JP6709103B2 (en) | Adhesive composition and adhesive sheet using the same | |
| CN113308203B (en) | Synthesis process of high-temperature-resistant photocuring acrylic foam adhesive tape | |
| CN110628361A (en) | Renewable pressure-sensitive adhesive and pressure-sensitive adhesive tape | |
| CN114958300A (en) | Bio-based pressure-sensitive adhesive and preparation method thereof | |
| CN108424731A (en) | A kind of preparation method of pressure sensitive adhesive | |
| JP7377997B1 (en) | Adhesive composition and adhesive sheet or tape | |
| CN109762486A (en) | A kind of pressure-sensitive adhesive making flexible PVC electrical adhesive tape and its processing method | |
| CN102101996A (en) | Pressure-sensitive adhesive used for cotton paper or non-woven fabrics and preparation method thereof | |
| JP7166052B2 (en) | Adhesive sheet | |
| CN102051148A (en) | Single-component environmentally-friendly electronic glue and application thereof | |
| CN103173143A (en) | Anisotropic conductive film and semiconductor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |