CN109651974B - Photo-curing pressure-sensitive adhesive and application thereof - Google Patents

Photo-curing pressure-sensitive adhesive and application thereof Download PDF

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CN109651974B
CN109651974B CN201811645980.5A CN201811645980A CN109651974B CN 109651974 B CN109651974 B CN 109651974B CN 201811645980 A CN201811645980 A CN 201811645980A CN 109651974 B CN109651974 B CN 109651974B
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sensitive adhesive
pressure
acrylic resin
mass
linking agent
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CN109651974A (en
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安明星
高昂
杨春强
朱敏芳
邹学良
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Suzhou Fineset Material Technology Co ltd
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    • 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]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • 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
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a photo-curing pressure-sensitive adhesive and application thereof, wherein the pressure-sensitive adhesive comprises acrylic resin syrup, a photoinitiator and a cross-linking agent, wherein the acrylic resin syrup comprises 15-40% of acrylic polymer with the weight average molecular weight of 50-200 ten thousand according to the mass percentage, the balance is monomers, and the monomers in the acrylic resin syrup comprise acrylic ester monomers with 1-18 carbon atoms and carboxyl-containing monomers; the dosage of the photoinitiator is 0.08-0.15% of the mass of the acrylic resin paste; the cross-linking agent comprises an epoxy cross-linking agent containing a phenylamine structure, and the dosage of the cross-linking agent is 0.005-3% of the mass of the acrylic resin syrup. The pressure-sensitive adhesive has long effective time, strong adhesive force, no organic solvent in use and thin coating thickness, and a product prepared by the pressure-sensitive adhesive has excellent constant load performance.

Description

Photo-curing pressure-sensitive adhesive and application thereof
Technical Field
The invention relates to the technical field of pressure-sensitive adhesives, in particular to a photo-curing pressure-sensitive adhesive and application thereof.
Background
Pressure-sensitive adhesives are pressure-sensitive adhesives, can be adhered to other surfaces under proper pressure when used, and are widely applied to industries such as printing, packaging, electronic products and the like at present due to the special adhesive characteristics of the pressure-sensitive adhesives. Electronic products such as mobile terminals of smart phones, tablet computers, automobile products, etc. have a tendency of being small, light, thin and efficient in production efficiency, and accordingly, the electronic products are required to use more and more polymer materials, and meanwhile, the adhesive products used by the materials are required to have high adhesive strength, so that firm adhesion is realized with a small adhesive area.
The common pressure-sensitive adhesives at present comprise solvent-type pressure-sensitive adhesives, water-based pressure-sensitive adhesives and hot-melt pressure-sensitive adhesives. With the strictness of environmental regulations and the gradual enhancement of environmental awareness of people, the solvent-based pressure-sensitive adhesive is more and more limited in use because the solvent is volatilized in the use process to pollute the environment; although the water-based pressure-sensitive adhesive has the advantages of no pollution and low cost, the water-based pressure-sensitive adhesive has the defects of poor water resistance, low stripping force and initial adhesion, poor low-temperature stability, high energy consumption and slow curing, and simultaneously, a large amount of water needs to be dried, so that the water-based pressure-sensitive adhesive is not beneficial to energy conservation and emission reduction; the hot melt type pressure sensitive adhesive is a third generation pressure sensitive adhesive product following solvent type and water-based pressure sensitive adhesive, and compared with the former two types of pressure sensitive adhesives, the hot melt type pressure sensitive adhesive has no solvent, is more beneficial to environmental protection and safe production, and has high production efficiency and relatively low production cost, but the heat resistance is poorer.
The photo-curing pressure-sensitive adhesive is a new type of pressure-sensitive adhesive, compared with the traditional solvent type pressure-sensitive adhesive, the photo-curing pressure-sensitive adhesive has no pollution caused by solvent volatilization in the using process, and compared with the water-based pressure-sensitive adhesive, the photo-curing pressure-sensitive adhesive has no performance problems of poor water resistance and the like; compared with the hot melt pressure sensitive adhesive, the heat resistance of the light-cured pressure sensitive adhesive is obviously better than that of the hot melt pressure sensitive adhesive due to the chemical crosslinking of the light-cured pressure sensitive adhesive in the curing process. Therefore, the photocuring pressure-sensitive adhesive has wide application prospect and research value.
In the process of preparing the light-cured pressure-sensitive adhesive, the commonly used ultraviolet light source is mainly a high-pressure mercury lamp, the wavelength bands of 254nm, 302nm, 313nm and 365nm in the emission spectrum of the high-pressure mercury lamp have good excitation effect on the photoinitiator, but the high-pressure mercury lamp has a plurality of defects in the use process; 1) the mercury lamp has high power and high energy consumption; 2) the heat is serious in the using process; 3) the starting is slow, and the preheating time is long; 4) continued use can cause mercury contamination. The UV-LED can obviously overcome the defects and has great application value. However, the spectral distribution is concentrated in the range from 365nm to 395nm, and the absorption spectrum of most photoinitiators cannot be matched therewith. Therefore, how to improve the production process of the photo-curing pressure-sensitive adhesive and improve the performance of the photo-curing pressure-sensitive adhesive is a problem to be solved by the technical personnel in the field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the photo-curing pressure-sensitive adhesive which has long effective time and good bonding strength.
In order to achieve the purpose, the invention adopts the technical scheme that: a photo-curing pressure-sensitive adhesive comprises the following components:
1) the acrylic resin syrup comprises 15-40% of acrylic polymer with the weight average molecular weight of 50-200 ten thousand by mass percent, and the balance of monomers, wherein the monomers in the acrylic resin syrup comprise acrylic ester monomers with 1-18 carbon atoms and carboxyl-containing monomers;
2) the amount of the photoinitiator is 0.08-0.15% of the mass of the acrylic resin slurry;
3) the cross-linking agent comprises an epoxy cross-linking agent containing an aniline structure, and the dosage of the cross-linking agent is 0.005-3% of the mass of the acrylic resin syrup.
Preferably, the raw materials of the acrylic resin syrup comprise an acrylate monomer with 1-18 carbon atoms, a carboxyl-containing monomer, a thermal initiator and a chain transfer agent, wherein the acrylate monomer accounts for 70-95% of the total mass of the monomers, and the carboxyl-containing monomer accounts for 5-30% of the total mass of the monomers; the dosage of the thermal initiator is 0.01-0.03% of the total mass of the monomers; the dosage of the chain transfer agent is 0.01-0.03 percent of the total mass of the monomers.
Further preferably, the acrylate monomer is isooctyl acrylate or a mixture of isooctyl acrylate and butyl acrylate, and the carboxyl group-containing monomer is acrylic acid.
Further preferably, the acrylic resin syrup is prepared according to the following steps: adding the acrylic ester monomer, the carboxyl-containing monomer and the chain transfer agent into a four-neck flask with a reflux condenser, stirring and mixing for 30min under nitrogen flow, then adding a thermal initiator, and reacting for 30min at the temperature of 60 ℃ to obtain the acrylic resin slurry.
Preferably, the acrylic resin syrup comprises 15-25% of acrylic polymer with the weight average molecular weight of 75-150 ten thousand by mass percentage, and the balance of monomer.
Preferably, the amount of the cross-linking agent is 0.05-0.15% of the mass of the acrylic resin syrup.
Preferably, the amount of the photoinitiator is 0.1-0.15% of the mass of the acrylic resin syrup.
Preferably, the photoinitiator is 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide.
Preferably, the epoxy cross-linking agent is selected from one of triglycidyl para-aminophenol, 4' -diaminodiphenylmethane epoxy resin and diglycidyl aniline.
Another object of the present invention is to provide a use of the above pressure-sensitive adhesive, wherein a layer of the pressure-sensitive adhesive is coated between two PET release films, and then the pressure-sensitive adhesive product is obtained by ultraviolet irradiation, wherein the ultraviolet irradiation is performed twice, the first irradiation is performed for 45s under a black light lamp, and the irradiation dose is 1mW cm-2Irradiating under black light for 180s for the second time with radiation dose of 3mW cm-2。
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the pressure-sensitive adhesive comprises acrylic resin slurry, a photoinitiator and a cross-linking agent, wherein the acrylic resin slurry comprises a monomer with high content ratio and a polymer with high molecular weight, the polymer is prepared from the monomer under the action of a thermal initiator and a chain transfer agent, the monomer comprises 70-95% of an acrylate monomer containing 1-18 carbon atoms and 5-30% of a carboxyl monomer according to the mass percentage, the pressure-sensitive adhesive prepared from the materials does not contain a solvent and is environment-friendly, and meanwhile, the epoxy cross-linking agent containing an aniline structure is adopted in the preparation process of the pressure-sensitive adhesive, so that the prepared pressure-sensitive adhesive and the product thereof have good load-setting performance and long effective time of the pressure-sensitive adhesive, the acrylic resin slurry prepared by adopting thermal reaction has short reaction time and can not generate a heating phenomenon, and can not cause a mercury pollution phenomenon generated by ultraviolet irradiation, is more environment-friendly.
Detailed Description
The technical solution of the present invention is further illustrated below with reference to specific examples.
A photo-curing pressure-sensitive adhesive comprises acrylic resin syrup, a photoinitiator and a cross-linking agent. The acrylic resin syrup comprises 15-40% of acrylic polymer with the weight average molecular weight of 50-200 ten thousand by mass percent, and the balance of monomers, wherein the monomers in the acrylic resin syrup comprise acrylic ester monomers with 1-18 carbon atoms and carboxyl-containing monomers; the dosage of the photoinitiator is 0.08-0.15 percent of the mass of the acrylic resin paste; the cross-linking agent comprises an epoxy cross-linking agent containing a aniline structure, and the dosage of the cross-linking agent is 0.005-3% of the mass of the acrylic resin syrup.
Specifically, the raw materials of the acrylic resin syrup comprise an acrylate monomer with 1-18 carbon atoms, a carboxyl-containing monomer, a thermal initiator and a chain transfer agent, wherein the acrylate monomer accounts for 70-95% of the total mass of the monomer, and the carboxyl-containing monomer accounts for 5-30% of the total mass of the monomer; the using amount of the thermal initiator is 0.01-0.03% of the total mass of the monomers; the dosage of the chain transfer agent is 0.01-0.03 percent of the total mass of the monomers.
The photoinitiator is 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide. The epoxy crosslinking agent containing aniline structure is one selected from triglycidyl p-aminophenol, 4' -diaminodiphenylmethane epoxy resin, diglycidyl aniline and epoxidized m-xylylenediamine.
Preparation of acrylic resin syrup
Here, the raw materials for preparing the acryl syrup are specifically: the acrylate monomer is selected from isooctyl acrylate or a mixture of isooctyl acrylate and butyl acrylate; acrylic acid is selected as the carboxyl-containing monomer; the thermal initiator is azodiisobutyronitrile; the chain transfer agent is n-dodecyl mercaptan.
The preparation method comprises the following specific steps:
acrylic Acid (AA), isooctyl ester (2-EHA), Butyl Acrylate (BA) and n-dodecyl mercaptan (NDM) are added into a four-neck flask with a reflux condenser, stirred and mixed for 30min under nitrogen flow, and then Azobisisobutyronitrile (AIBN) is added to react for 30min at the temperature of 60 ℃ to obtain acrylic resin slurry. The thermal reaction is adopted to prepare the acrylic resin slurry, the reaction time is short, the serious heating condition is avoided, and the mercury pollution phenomenon is avoided compared with the ultraviolet light irradiation reaction.
The obtained acryl syrup was subjected to a viscosity test by a viscosity test method, a weight average molecular weight of the acryl polymer contained in the acryl syrup was measured by a GPC measurement method, and a content ratio of the acryl polymer contained in the acryl syrup was measured by a non-volatile component amount measuring method. Specifically, the amounts of the components added and the measurement results are shown in table 1, and the specific detection methods are as follows.
Viscosity measuring method
A500 ml bottle containing acryl syrup was immersed in a constant temperature water at 25 ℃ and left standing for 12 hours, and then measured according to a measurement method of a B-type viscometer.
GPC measurement method
A measuring device: HLC-8120 GPC (manufactured by Tosoh Corporation)
GPC column composition: the following 5 columns (all manufactured by Tosoh Corp.)
(1) TSK-GEL HXL-H (guard column)
(2)TSK-GEL G 7000 H X L.
(3)TSK-GEL GMHXL
(4)TSK-GEL GMHXL
(5)TSK-GEL G 2500 H X L.
Sample concentration: diluting with tetrahydrofuran to 1.0mg/cm3
Mobile phase solvent: tetrahydrofuran (THF)
Flow rate: 1.0cm3/min
Column temperature: 40 deg.C
Method for measuring non-volatile component amount
1g of the acrylic resin syrup was put into a precisely weighed tin plate (n1), the total weight was precisely weighed (n2), and then heated at 105 ℃ for 3 hours, and then the tin plate was left in a desiccator at room temperature for 1 hour, and then precisely weighed again, and the total weight after heating was measured (n 3). By using the obtained weight measurement values (n1 to n3), the amount of the nonvolatile component was calculated from the following formula (1).
The amount of non-volatile component nV (wt%) (-) of formula (1)
100 × [ weight after heating (n3-n 1)/weight before heating (n2-n1) ]
TABLE 1
Figure BDA0001932067550000051
As can be seen from Table 1, when the amounts of the components added to the monomers are the same, the addition of the chain transfer agent (NDM) is reduced, and when A-2 and A-4 are compared, the viscosity of the acryl syrup can be increased, and the weight average molecular weight of the polymer can be increased;
under the condition that the adding amount of each component in the monomer is the same, the adding amount of the chain transfer agent (NDM) and the thermal initiator is too much, compared with A-5 and A-6, the viscosity of the acrylic resin syrup can be greatly reduced, the content ratio of the polymer in the acrylic resin syrup can be increased, and the weight average molecular weight of the polymer can be greatly reduced;
under the condition that the addition amount of the cross-linking agent is the same as that of the thermal initiator, the use amounts of AA and BA are properly increased, and the viscosity of the acrylic resin syrup can be improved and the weight average molecular weight of the polymer can be improved by comparing A-4 with A-5.
Under the condition that the adding amount of AA in the monomer is not changed, the using amount of BA is increased, and meanwhile, a small amount of chain transfer agent (NDM) is increased, compared with A-1 and A-3, the viscosity of the acrylic resin syrup can be increased, and the weight average molecular weight of the polymer is reduced.
Preparation of pressure-sensitive adhesive
The embodiment provides a preparation method of a pressure-sensitive adhesive, which comprises the following specific steps:
according to the mass portion, the acrylic resin syrup is taken as 100, the photoinitiator and the cross-linking agent are added into the acrylic resin syrup according to the mass ratio, the conditions of all components in the acrylic resin syrup refer to table 1, then the pressure-sensitive adhesive is obtained through stirring and vacuum defoaming treatment, and the specific mixture ratio of the photoinitiator and the cross-linking agent is referred to table 2.
TABLE 2
Figure BDA0001932067550000061
In the above table, TPO is 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, JeR603 is triglycidyl p-aminophenol, JeR604 is 4,4' -diaminodiphenylmethane epoxy resin, GAN is diglycidylaniline, EPALLOY GA-240 is epoxidized m-xylylenediamine, and TMPTA is trimethylolpropane triacrylate.
Preparation of pressure-sensitive adhesive product
According to the pressure-sensitive adhesive prepared in each example or comparative example in table 2, a pressure-sensitive adhesive article was prepared by the following procedure. First, a coating layer (thickness of 300 μm) of a pressure-sensitive adhesive prepared by each example and comparative example in Table 2 was applied on the surface of a polyethylene terephthalate PET release film (thickness of 50 μm) using a doctor blade; subsequently, a PET release film (thickness of 50 μm) was further laminated on the surface of the coating layer to obtain a laminated sheet. Thereafter, the laminated sheet is irradiated with ultraviolet rays to polymerize the photo-curable pressure-sensitive adhesive constituting the coating layer. Thus, a pressure-sensitive adhesive sheet containing a photo-curable pressure-sensitive adhesive between two PET release films was obtained. Specifically, ultraviolet rays are adopted for irradiation twice, the first irradiation is carried out for 45s under a black light lamp, and the radiation dose is 1mW cm-2Irradiating under black light for 180s for the second time with radiation dose of 3mW cm-2And peeling off the PET peeling film on one side to obtain the pressure-sensitive adhesive tape.
The pressure-sensitive adhesives of the respective examples and comparative examples in Table 2 were tested for the effective time in the following manner. See table 3 for test data. Meanwhile, after the pressure-sensitive adhesive tapes prepared according to the pressure-sensitive adhesives in table 2 were respectively placed in a thermostat at 40 ℃ for 3 days, at 60 ℃ for 1 minute, and after being placed for one month for aging test, the gel fraction, the adhesion constant load test, the holding power, and the ball tack were evaluated, and the specific test results are shown in table 4. The details of each evaluation method are as follows:
testing of the effective time
The pot life is defined as the measured evaluation of the viscosity of the pressure-sensitive adhesive immediately after preparation and after 2,4,6 and 8 hours of standing, respectively. Specifically, the viscosity was measured by immersing a 500ml bottle containing a pressure-sensitive adhesive in a constant temperature water bath at 23 ℃ and then measuring according to the measurement method of a B-type viscometer, and the measurement results are shown in table 3.
The judgment criteria of the effective time shown in table 3 are as follows:
o: the viscosity change after 8 hours is below 120% based on the initial viscosity (100%)
And (delta): the change in viscosity after 8 hours was more than 120%, based on the initial viscosity (100%)
X: gelation from just after preparation to 8 hours
Adhesion test
The adhesive force was measured by backing a 25 μm PET film on the back surface of the adhesive tape and measuring the peel adhesion to the adherend SUS in the direction of 180 ° in an environment of 23 ℃ after leaving the pressure-sensitive adhesive tape in a thermostat at 40 ℃ for 3 days or at 60 ℃ for 1 month according to the test method of JIS Z0237 pressure-sensitive adhesive tape.
Constant load test
After the pressure-sensitive adhesive tape was left to stand in a thermostat at 40 ℃ for 3 days or at 60 ℃ for 1 month, the back surface of the pressure-sensitive adhesive tape was backed with a 25 μm PET film and cut into a size of 20 × 50mm to prepare a test piece. The PET release film was peeled from the test piece, adhered to a SUS plate, and a 1kg weight was hung at a temperature of 80 ℃ in a direction of 90 ℃ for 60 minutes, and then the peeling distance (mm) or the falling time was measured.
Retention force test
According to the test method of JIS Z0237 pressure sensitive adhesive tape, a 25 μm PET film was backed on the back surface of the pressure sensitive adhesive tape, a SUS steel plate was attached with an attaching area of 25X 25mm, and the displacement distance or the falling time after 60min was measured with a 1kg weight hung at 80 ℃.
TABLE 3
Figure BDA0001932067550000081
As can be seen from Table 3, comparative examples 2, 3 and 4 showed gelation, and thus it was judged that when the acryl syrup having a high molecular weight polymer was used, the time for which the pressure-sensitive adhesive was obtained was poor due to its high activity and gelation was easily caused by using epoxidized m-xylylenediamine EPALLOY GA-240 as a crosslinking agent, and it was also shown from Table 3 that the viscosity of the pressure-sensitive adhesive was low, thereby facilitating uniform coating during the coating process.
TABLE 4
Figure BDA0001932067550000082
Figure BDA0001932067550000091
As can be seen from Table 4, when epoxidized m-xylylenediamine (EPALLOY GA-240) and trimethylolpropane triacrylate (TMPTA) were used as the crosslinking agents, they fell after standing in a thermostat at 40 ℃ for 3 days or at 60 ℃ for 1 month, and therefore, the preferred crosslinking agents herein were triglycidyl p-aminophenol (jER603), 4' -diaminodiphenylmethane epoxy resin (jER604), diglycidylaniline (GAN). From the above table, it can also be seen that the pressure-sensitive adhesive of the present invention has a small coating thickness during the application process, thereby greatly reducing the thickness of the electronic product.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (7)

1. The photo-curing pressure-sensitive adhesive is characterized by comprising the following components:
1) the acrylic resin syrup comprises 15-40% of acrylic polymer with the weight average molecular weight of 50-200 ten thousand according to mass percentage, raw materials of the acrylic resin syrup comprise acrylic ester monomer with 1-18 carbon atoms, carboxyl-containing monomer, thermal initiator and chain transfer agent, the acrylic ester monomer accounts for 70-95% of the total mass of the monomers, and the carboxyl-containing monomer accounts for 5-30% of the total mass of the monomers; the amount of the thermal initiator is 0.01-0.03% of the total mass of the monomers, the amount of the chain transfer agent is 0.01-0.03% of the total mass of the monomers, the acrylate monomer is isooctyl acrylate or a mixture of isooctyl acrylate and butyl acrylate, and the carboxyl-containing monomer is acrylic acid;
2) the photoinitiator, wherein the dosage of the photoinitiator is 0.08-0.15% of the mass of the acrylic resin slurry;
3) the cross-linking agent comprises an epoxy cross-linking agent containing an aniline structure, the dosage of the cross-linking agent is 0.005% -3% of the mass of the acrylic resin slurry, and the epoxy cross-linking agent is selected from one of triglycidyl p-aminophenol, 4' -diaminodiphenylmethane epoxy resin and diglycidyl aniline.
2. The light-curable pressure-sensitive adhesive according to claim 1, wherein the acryl syrup is prepared by the following steps: adding the acrylic ester monomer, the carboxyl-containing monomer and the chain transfer agent into a four-neck flask with a reflux condenser, stirring and mixing for 30min under nitrogen flow, then adding a thermal initiator, and reacting for 30min at the temperature of 60 ℃ to obtain the acrylic resin slurry.
3. The light-cured pressure-sensitive adhesive according to claim 1, wherein the acrylic resin syrup comprises 15 to 25 mass percent of acrylic polymer with an average molecular weight of 75 to 150 ten thousand.
4. The photo-curing pressure-sensitive adhesive according to claim 1, wherein the amount of the cross-linking agent is 0.05-0.15% of the mass of the acrylic resin syrup.
5. The photo-curable pressure-sensitive adhesive according to claim 1, wherein the amount of the photo-initiator is 0.1% to 0.15% by mass of the acryl syrup.
6. The light-curable pressure-sensitive adhesive of claim 1 wherein the photoinitiator is 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide.
7. Use of a photocurable pressure-sensitive adhesive according to any of claims 1 to 6, characterized in that a layer of said pressure-sensitive adhesive is applied between two PET release films and the pressure-sensitive adhesive article is obtained by UV irradiation, wherein the UV irradiation is carried out twice, the first irradiation is carried out under a black light for 45s, and the irradiation dose is 1 mW-cm-2Irradiating under black light for 180s for the second time with radiation dose of 3mW cm-2。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1434844A (en) * 1999-12-22 2003-08-06 综研化学株式会社 Acrylic polymer compositions, acrylic pressure-sensitive adhesion tapes and process for producing the same
CN103849332A (en) * 2012-11-30 2014-06-11 综研化学株式会社 Adhesive composition
CN106414642A (en) * 2014-05-29 2017-02-15 3M创新有限公司 Acrylic adhesive composition with controlled molecular weight

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1434844A (en) * 1999-12-22 2003-08-06 综研化学株式会社 Acrylic polymer compositions, acrylic pressure-sensitive adhesion tapes and process for producing the same
CN103849332A (en) * 2012-11-30 2014-06-11 综研化学株式会社 Adhesive composition
CN106414642A (en) * 2014-05-29 2017-02-15 3M创新有限公司 Acrylic adhesive composition with controlled molecular weight

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