CN112375516A - Special high-viscosity high-temperature-resistant pressure-sensitive adhesive for electronic products and preparation and protective film thereof - Google Patents
Special high-viscosity high-temperature-resistant pressure-sensitive adhesive for electronic products and preparation and protective film thereof Download PDFInfo
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- 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]
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- C09J2433/00—Presence of (meth)acrylic polymer
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- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
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Abstract
The invention belongs to the technical field of special functional thin film materials, and discloses a high-viscosity high-temperature-resistant pressure-sensitive adhesive special for electronic products, a preparation method and application thereof, and a protective film based on the high-viscosity high-temperature-resistant pressure-sensitive adhesive. The formula of the high-viscosity high-temperature-resistant pressure-sensitive adhesive special for electronic products comprises alkynyl-containing high-viscosity acrylate copolymer, azidonaphthalene-containing ring-type tetrafunctional epoxy resin and a catalyst. The alkynyl-containing high-viscosity acrylate copolymer takes high-temperature-resistant nitrine-containing naphthalene ring type tetrafunctional epoxy resin as a cross-linking agent, and reacts to generate high-temperature-resistant 1, 4-disubstituted-1, 2, 3-triazole cross-linking points by adopting an alkynyl-nitrine click chemical ring addition cross-linking system, so that the pressure-sensitive adhesive with high viscosity, excellent high temperature resistance is obtained, and the technical problem of insufficient high-temperature resistance of the traditional acrylic pressure-sensitive adhesive is effectively solved. Meanwhile, the high-viscosity high-temperature-resistant pressure-sensitive adhesive has excellent foam discharging and attaching performances, and the temperature resistance can reach 230 ℃; the high-viscosity high-temperature-resistant pressure-sensitive protective film can be obtained based on the method, and can be applied to the field of reflow soldering processing of specific electronic products.
Description
Technical Field
The invention belongs to the technical field of special functional thin film materials, and particularly relates to a high-viscosity high-temperature-resistant pressure-sensitive adhesive special for electronic products, a preparation method and application thereof, and a protective film based on the high-viscosity high-temperature-resistant pressure-sensitive adhesive.
Background
The electronic product protective film can be applied to the production, processing and transportation processes of electronic devices, and can prevent the surfaces of the electronic devices from being scratched or polluted in the processing process; after protection, the protective film is required to be completely torn off and not to remain on the surface of the glass, so that the film material is polluted. With the rapid development of electronic product production and processing technology, the requirements for the performance of the protective film are higher. For example, in the PVD process of the glass of the tablet personal computer and the mobile phone, the protective film is generally required to be resistant to temperature of 1-2h at the high temperature of 160-220 ℃, so as to meet the high temperature resistant requirement of glass electroplating, and the protective film has no residue after being used and is easy to remove.
The high-temperature resistant protective films widely used at present comprise polyurethane adhesive protective films, silicon-based protective films and acrylic-based protective films. The polyurethane adhesive-based protective film has the excellent characteristics of heat resistance, toughness and the like, but the viscous force is quickly improved at high temperature and is not easy to remove. The silicon-based protective film has the characteristics of easy peeling, no residual glue and stable viscosity, but silicon transfer is easy to occur, and the surface characteristics of the protected material are influenced. The acrylic-based protective film has the characteristics of high adsorbability, automatic bubble removal and the like, but has poor temperature resistance. In order to further improve the temperature resistance of the acrylic-based protective film, an acrylate system is often modified to improve the temperature resistance. Chinese patent application No. 201910576982.1 developed a high temperature resistant acrylate protective film based on an acrylate polymer system, which has high tack and tack-free properties at 150 ℃. The Chinese patent application number of 201811216970X uses isocyanate and metal ions for double crosslinking to obtain the protective film capable of resisting the high temperature of 160 ℃. The Chinese patent application No. 201810505179.4 adopts a controllable active polymerization method (RAFT polymerization) to carry out polymerization reaction, so that the high-temperature-resistant pressure-sensitive adhesive with excellent performance is obtained, and the prepared protective film resists the high temperature of 180 ℃.
However, the existing high-temperature resistant acrylate protective film is difficult to exceed the high temperature of 180 ℃, cannot meet the requirements of production and processing protection of more electronic devices at the temperature higher than 180 ℃, and is easy to have a degumming phenomenon to pollute the surfaces of the electronic devices. Meanwhile, shape changes such as internal shrinkage and curling are likely to occur at high temperature. The high-viscosity high-temperature-resistant pressure-sensitive adhesive has better laminating property and is suitable for the field of reflow soldering processing of electronic products.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide the special high-viscosity high-temperature-resistant pressure-sensitive adhesive for the electronic product.
The invention also aims to provide a preparation method of the special high-viscosity high-temperature-resistant pressure-sensitive adhesive for the electronic product.
The invention further aims to provide application of the special high-viscosity high-temperature-resistant pressure-sensitive adhesive for the electronic product.
The invention further aims to provide a high-viscosity high-temperature-resistant pressure-sensitive protective film based on the pressure-sensitive adhesive.
The purpose of the invention is realized by the following scheme:
a high-viscosity high-temperature-resistant pressure-sensitive adhesive special for electronic products comprises an alkynyl-containing high-viscosity acrylate copolymer, a tetrafunctional epoxy resin containing azidonaphthalene and a catalyst.
The mass ratio of the alkyne-containing high-viscosity acrylate copolymer to the azide-naphthalene-containing ring type tetrafunctional epoxy resin is preferably 100:0.1-50: 10.
The catalyst is a click chemistry catalytic system, such as a mixture of ascorbic acid and copper sulfate, and the mass ratio of the ascorbic acid to the copper sulfate is preferably 5: 1. The amount of catalyst used is a catalytic amount.
Further, the alkynyl-containing high-viscosity acrylate copolymer is obtained by reacting 2-ethylhexyl acrylate, butyl acrylate, N-dimethylacrylamide, 2- (2-naphthylthio) ethyl 2-acrylate, 2-bromoethyl acrylate and propargyl alcohol in a solvent system.
The mass ratio of 2-ethylhexyl acrylate, butyl acrylate, N-dimethylacrylamide, 2- (2-naphthylthio) ethyl 2-acrylate, 2-bromoethyl acrylate and propargyl alcohol used is preferably (100-: (20-70): (5-50): (5-50): (1-40): (1-50).
The reaction is preferably carried out at from 70 to 120 ℃.
The solvent is an organic solvent, preferably at least one of dimethylformamide, tetrahydrofuran, toluene and ethyl acetate.
Furthermore, the alkynyl-containing high-viscosity acrylate copolymer is synthesized by polymerizing 2-ethylhexyl acrylate, butyl acrylate, N-dimethylacrylamide, 2- (2-naphthylthio) ethyl acrylate and 2-bromoethyl acrylate in a solvent system to react A, and then adding propargyl alcohol to react B.
The polymerization reaction A is carried out under the initiation of a free radical initiator.
The radical initiator may be dibenzoyl peroxide and azobisisobutyronitrile.
The initiator is used in a conventional amount. For example, it may be 0.01 to 1% by mass based on the total mass of the reaction system.
The polymerization reaction A is preferably carried out for a period of 8 to 40 hours.
The reaction B is carried out under the catalysis of sodium tert-butoxide; the amount used is a catalytic amount.
The reaction time of B is preferably 20-50 h.
And filtering after the reaction B to obtain the alkynyl-containing high-viscosity acrylate copolymer solution.
The viscosity range of the alkyne-containing high viscosity acrylate copolymer is 10000-50000 cps.
Further, the azide-containing naphthalene ring type tetrafunctional epoxy resin is obtained by reacting naphthalene ring type tetrafunctional epoxy resin, sodium azide and aluminum trichloride in a solvent system.
The naphthalene ring type tetrafunctional epoxy resin can be selected from HP-4700 produced by Nippon DIC company.
The mass ratio of the naphthalene ring type tetrafunctional epoxy resin, sodium azide and aluminum trichloride is preferably (30-100): (1-20): (0.1-0.5).
The reaction is preferably carried out at from 40 to 80 ℃.
The solvent is an organic solvent, and is preferably dimethylformamide.
The reaction time is preferably 20 to 40 h.
The invention also provides a preparation method of the special high-viscosity high-temperature-resistant pressure-sensitive adhesive for the electronic product, which is characterized in that the alkyne-containing high-viscosity acrylate copolymer, the azide-containing naphthalene ring type tetrafunctional epoxy resin and the catalyst are uniformly mixed in inert atmosphere. When in use, the special high-viscosity high-temperature-resistant pressure-sensitive adhesive for the electronic product is coated on a substrate and heated to generate an alkynyl-azide crosslinking reaction to form an adhesive pressing layer.
The high-viscosity high-temperature-resistant pressure-sensitive adhesive component special for the electronic product comprises an alkynyl-containing high-viscosity acrylate copolymer and azido naphthalene-containing ring-type tetrafunctional epoxy resin, wherein the alkynyl-containing high-viscosity acrylate copolymer adopts 2-acrylic acid 2- (2-naphthylthio) ethyl ester as a monomer, is a naphthyl high-temperature-resistant monomer, and shows better temperature resistance compared with the traditional used acrylic monomer, so that the temperature resistance of matrix resin is improved; in the using process, high-temperature-resistant azide-containing naphthalene ring type tetrafunctional epoxy resin is used as a cross-linking agent, an alkynyl-azide click chemical ring addition cross-linking system is adopted, so that the two copolymers react to generate high-temperature-resistant 1, 4-disubstituted-1, 2, 3-triazole cross-linking points, the temperature resistance of the acrylate pressure-sensitive adhesive is improved, the pressure-sensitive adhesive with high viscosity and excellent high temperature resistance is obtained, and the technical problem that the high-temperature resistance of the traditional acrylic pressure-sensitive adhesive is insufficient is effectively solved.
Furthermore, the invention also provides a high-viscosity high-temperature-resistant pressure-sensitive protective film based on the pressure-sensitive adhesive, which comprises a polyethylene terephthalate release film with the thickness of 20-75 mu m, a pressure-sensitive adhesive layer with the thickness of 5-50 mu m and a polyimide film with the thickness of 5-100 mu m from bottom to top, wherein the pressure-sensitive adhesive layer is formed by coating the special high-viscosity high-temperature-resistant pressure-sensitive adhesive for electronic products.
Further, the invention also provides a preparation method of the high-viscosity high-temperature-resistant pressure-sensitive protective film, which comprises the following process steps:
under the protection of nitrogen, the special high-viscosity high-temperature-resistant pressure-sensitive adhesive for the electronic product is coated on a polyimide film, is placed at 80-200 ℃ for heat preservation, drying and curing for 5-60min to form a pressure-sensitive adhesive layer, a polyethylene glycol terephthalate release film is attached to the front surface of the pressure-sensitive adhesive layer, is placed at 40-60 ℃, and is subjected to post curing for 24-100 hours to obtain the high-viscosity high-temperature-resistant pressure-sensitive protective film.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the special high-viscosity high-temperature-resistant pressure-sensitive adhesive for the electronic product, 2- (2-naphthylthio) ethyl 2-acrylate is a naphthyl high-temperature-resistant monomer, and compared with a traditional acrylic monomer, the special high-viscosity high-temperature-resistant pressure-sensitive adhesive has better temperature resistance, so that the temperature resistance of matrix resin is improved.
(2) According to the invention, the alkynyl-containing high-viscosity acrylate copolymer and the azide-containing naphthalene ring type tetrafunctional epoxy resin are synthesized firstly, an alkynyl-azide click chemistry ring addition crosslinking system is adopted, and the high-temperature-resistant naphthalene ring type tetrafunctional epoxy resin is introduced to generate the high-temperature-resistant 1, 4-disubstituted-1, 2, 3-triazole crosslinking points, so that the temperature resistance of the acrylate pressure-sensitive adhesive is improved.
(3) The high-viscosity high-temperature-resistant pressure-sensitive adhesive has excellent bubble removal and bonding performance, the temperature resistance is 180-230 ℃, and can reach 230 ℃, and the high-temperature-resistant requirement of specific reflow soldering processing is met.
Detailed Description
The present invention is specifically described below with reference to examples in order to facilitate understanding of the present invention by those skilled in the art. It should be particularly noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as non-essential improvements and modifications to the invention may occur to those skilled in the art, which fall within the scope of the invention as defined by the appended claims. Meanwhile, the raw materials mentioned below are not specified in detail and are all commercial products; the process steps or preparation methods not mentioned in detail are all process steps or preparation methods known to the person skilled in the art.
Example 1
A high-viscosity high-temperature-resistant pressure-sensitive adhesive special for electronic products and a protective film thereof are disclosed, and the preparation process comprises the following steps:
the method comprises the following steps: synthesis of alkynyl-containing high-viscosity acrylate copolymer
200 parts of 2-ethylhexyl acrylate, 30 parts of butyl acrylate, 10 parts of N, N-dimethylacrylamide, 25 parts of 2- (2-naphthylthio) ethyl 2-acrylate, 10 parts of 2-bromoethyl acrylate, 0.1 part of dibenzoyl peroxide, 0.05 part of azobisisobutyronitrile, 100 parts of ethyl acetate and 60 parts of tetrahydrofuran are mixed according to the mass parts of the raw materials, the temperature is controlled at 85 ℃, free radical polymerization reaction is carried out for 15 hours, 12 parts of sodium tert-butoxide and 8 parts of propargyl alcohol are added for reaction for 25 hours, and after filtration, a high viscosity acrylate copolymer solution containing alkynyl with the viscosity of 38000cps is obtained.
Step two: synthesis of nitrine naphthalene ring-containing tetrafunctional epoxy resin
Adding 30 parts of naphthalene ring type tetrafunctional epoxy resin (HP-4700), 3 parts of sodium azide and 0.1 part of aluminum trichloride into 40 parts of dimethylformamide according to the mass parts of raw materials, reacting for 30 hours, and filtering to obtain the tetrafunctional epoxy resin containing the azide and naphthalene ring type.
Step three: high-viscosity high-temperature-resistant pressure-sensitive adhesive special for electronic products
According to the mass parts, the alkynyl-containing high-viscosity acrylate copolymer prepared in the step one and the azido naphthalene-containing ring-type tetrafunctional epoxy resin prepared in the step two are mixed according to the mass ratio of 100: and 3, mixing the components in total 400 parts, adding 1 part of ascorbic acid and 0.2 part of copper sulfate under the protection of nitrogen, and uniformly mixing to obtain the special high-viscosity high-temperature-resistant pressure-sensitive adhesive for electronic products.
Step four: preparation of high-viscosity high-temperature-resistant protective film special for electronic product
And (3) coating the special high-viscosity high-temperature-resistant pressure-sensitive adhesive for the electronic product synthesized in the step three on a polyimide film with the thickness of 12.5 microns under the protection of nitrogen, placing at 185 ℃, preserving heat, drying and curing for 20min to form a pressure-sensitive adhesive layer with the thickness of 21 microns, attaching a polyethylene glycol terephthalate release film with the thickness of 50 microns on the front surface of the pressure-sensitive adhesive layer, placing at 60 ℃, and performing after-curing for 60 hours to obtain the high-viscosity high-temperature-resistant pressure-sensitive protective film.
Example 2
A high-viscosity high-temperature-resistant pressure-sensitive adhesive special for electronic products and a protective film thereof are disclosed, and the preparation process comprises the following steps:
the method comprises the following steps: synthesis of alkynyl-containing high-viscosity acrylate copolymer
200 parts of 2-ethylhexyl acrylate, 60 parts of butyl acrylate, 20 parts of N, N-dimethylacrylamide, 40 parts of 2- (2-naphthylthio) ethyl 2-acrylate, 20 parts of 2-bromoethyl acrylate, 0.2 part of dibenzoyl peroxide, 0.1 part of azobisisobutyronitrile, 100 parts of ethyl acetate and 100 parts of dimethylformamide are mixed according to the mass parts of the raw materials, the temperature is controlled at 95 ℃, free radical polymerization reaction is carried out for 20 hours, 23 parts of sodium tert-butoxide and 14 parts of propargyl alcohol are added, the reaction is carried out for 23 hours, and after filtration, a high viscosity acrylate copolymer solution containing alkynyl with the viscosity of 27000cps is obtained.
Step two: synthesis of nitrine naphthalene ring-containing tetrafunctional epoxy resin
Adding 50 parts of naphthalene ring type tetrafunctional epoxy resin (HP-4700), 5 parts of sodium azide and 0.2 part of aluminum trichloride into 40 parts of dimethylformamide according to the mass parts of raw materials, reacting for 30 hours, and filtering to obtain the tetrafunctional epoxy resin containing the azide and naphthalene ring type.
Step three: high-viscosity high-temperature-resistant pressure-sensitive adhesive special for electronic products
Mixing the alkynyl-containing high-viscosity acrylate copolymer prepared in the step one and the azido naphthalene-containing ring-type tetrafunctional epoxy resin prepared in the step two according to the mass ratio of 100:6 to obtain 400 parts, and adding 2 parts of ascorbic acid and 0.4 part of copper sulfate under the protection of nitrogen to uniformly mix to obtain the high-viscosity high-temperature-resistant pressure-sensitive adhesive special for electronic products.
Step four: preparation of high-viscosity high-temperature-resistant protective film special for electronic product
And (3) coating the special high-viscosity high-temperature-resistant pressure-sensitive adhesive for the electronic product synthesized in the step three on a polyimide film with the thickness of 20 micrometers under the protection of nitrogen, placing at 190 ℃, preserving heat, drying and curing for 25min to form a pressure-sensitive adhesive layer with the thickness of 15 micrometers, attaching a polyethylene glycol terephthalate release film with the thickness of 10 micrometers on the front surface of the pressure-sensitive adhesive layer, placing at 60 ℃, and performing after-curing for 100 hours to obtain the high-viscosity high-temperature-resistant pressure-sensitive protective film.
Example 3
A high-viscosity high-temperature-resistant pressure-sensitive adhesive special for electronic products and a protective film thereof are disclosed, and the preparation process comprises the following steps:
the method comprises the following steps: synthesis of alkynyl-containing high-viscosity acrylate copolymer
According to the mass parts of the raw materials, 220 parts of 2-ethylhexyl acrylate, 40 parts of butyl acrylate, 30 parts of N, N-dimethylacrylamide, 45 parts of 2- (2-naphthylthio) ethyl 2-acrylate, 15 parts of 2-bromoethyl acrylate, 0.3 part of dibenzoyl peroxide, 0.2 part of azobisisobutyronitrile, 120 parts of ethyl acetate and 60 parts of toluene are mixed, the temperature is controlled at 85 ℃, free radical polymerization reaction is carried out for 18 hours, 12 parts of sodium tert-butoxide and 17 parts of propargyl alcohol are added, reaction is carried out for 26 hours, and after filtration, a high viscosity acrylate copolymer solution containing alkynyl is obtained, wherein the viscosity is 23000 cps.
Step two: synthesis of nitrine naphthalene ring-containing tetrafunctional epoxy resin
Adding 80 parts of naphthalene ring type tetrafunctional epoxy resin (HP-4700), 10 parts of sodium azide and 0.5 part of aluminum trichloride into 40 parts of dimethylformamide according to the mass parts of raw materials, reacting for 30 hours, and filtering to obtain the tetrafunctional epoxy resin containing the azide and naphthalene ring type.
Step three: high-viscosity high-temperature-resistant pressure-sensitive adhesive special for electronic products
Mixing the alkynyl-containing high-viscosity acrylate copolymer prepared in the step one and the azido naphthalene-containing ring-type tetrafunctional epoxy resin prepared in the step two according to the mass ratio of 100:8 to obtain 400 parts, and adding 3 parts of ascorbic acid and 0.6 part of copper sulfate under the protection of nitrogen to uniformly mix to obtain the high-viscosity high-temperature-resistant pressure-sensitive adhesive special for electronic products.
Step four: preparation of high-viscosity high-temperature-resistant protective film special for electronic product
And (3) coating the special high-viscosity high-temperature-resistant pressure-sensitive adhesive for the electronic product synthesized in the step three on a polyimide film with the thickness of 50 micrometers under the protection of nitrogen, placing at 195 ℃, keeping the temperature, drying and curing for 30min to form a pressure-sensitive adhesive layer with the thickness of 25 micrometers, attaching a polyethylene glycol terephthalate release film with the thickness of 40 micrometers on the front surface of the pressure-sensitive adhesive layer, placing at 50 ℃, and performing after-curing for 80 hours to obtain the high-viscosity high-temperature-resistant pressure-sensitive protective film.
Example 4
A high-viscosity high-temperature-resistant pressure-sensitive adhesive special for electronic products and a protective film thereof are disclosed, and the preparation process comprises the following steps:
the method comprises the following steps: synthesis of alkynyl-containing high-viscosity acrylate copolymer
According to the mass parts of the raw materials, 240 parts of 2-ethylhexyl acrylate, 50 parts of butyl acrylate, 40 parts of N, N-dimethylacrylamide, 50 parts of 2- (2-naphthylthio) ethyl 2-acrylate, 20 parts of 2-bromoethyl acrylate, 0.4 part of dibenzoyl peroxide, 0.3 part of azobisisobutyronitrile, 160 parts of ethyl acetate and 40 parts of dimethylformamide are mixed, the temperature is controlled at 90 ℃, free radical polymerization reaction is carried out for 23 hours, 14 parts of sodium tert-butoxide and 27 parts of propargyl alcohol are added, reaction is carried out for 28 hours, and after filtration, a high viscosity acrylate copolymer solution containing alkynyl is obtained, wherein the viscosity is 12000 cps.
Step two: synthesis of nitrine naphthalene ring-containing tetrafunctional epoxy resin
Adding 100 parts of naphthalene ring type tetrafunctional epoxy resin (HP-4700), 15 parts of sodium azide and 0.5 part of aluminum trichloride into 40 parts of dimethylformamide according to the mass parts of raw materials, reacting for 30 hours, and filtering to obtain the tetrafunctional epoxy resin containing the azide and naphthalene ring type.
Step three: high-viscosity high-temperature-resistant pressure-sensitive adhesive special for electronic products
Mixing the alkynyl-containing high-viscosity acrylate copolymer prepared in the step one and the azido naphthalene-containing ring-type tetrafunctional epoxy resin prepared in the step two according to the mass ratio of 100:10 to obtain 400 parts, and adding 4 parts of ascorbic acid and 0.8 part of copper sulfate under the protection of nitrogen to uniformly mix to obtain the high-viscosity high-temperature-resistant pressure-sensitive adhesive special for electronic products.
Step four: preparation of high-viscosity high-temperature-resistant protective film special for electronic product
And (3) coating a 25-micron polyimide film on the special high-viscosity high-temperature-resistant pressure-sensitive adhesive for the electronic product synthesized in the step three under the protection of nitrogen, placing at 200 ℃, preserving heat, drying and curing for 10min to form a 20-micron pressure-sensitive adhesive layer, attaching a 20-micron polyethylene terephthalate release film on the front surface of the pressure-sensitive adhesive layer, placing at 50 ℃, and performing post-curing for 70 hours to obtain the high-viscosity high-temperature-resistant pressure-sensitive protective film.
Example 5: performance testing
The pressure-sensitive adhesive tape finished products obtained in the above 4 examples were subjected to a test of a 180 ° peel force of a sample, a high temperature performance index test and a high and low temperature cycle index test with reference to a general method of a protective film. 180 DEG peel force was tested with reference to the GB/T7122-1996 standard. The specific test method of the high-temperature performance index comprises the steps of adhering a high-temperature resistant protective film on glass, placing the glass in an oven with a set specific temperature for baking for 2 hours, taking out the glass, cooling the glass, uncovering the protective film, observing whether residual glue exists on the surface of the glass, and observing the denaturation condition of each sample. The high-low temperature cycle index test is to stick a high-temperature resistant protective film on glass, place the glass in an environment of 10-230 ℃, carry out variable temperature cycle at 1 ℃/min for 10h, take out the glass, cool the glass, uncover the protective film, and observe whether the surface of the glass has residual glue. All test data comparisons are shown in table 1 below.
As can be seen from the data in Table 1, the temperature resistance of the high-temperature-resistant pressure-sensitive protective film prepared from the high-temperature-resistant pressure-sensitive adhesive synthesized by the invention can reach 230 ℃.
TABLE 1 Properties of high-viscosity high-temperature-resistant protective film specially used for electronic products
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A high-viscosity high-temperature-resistant pressure-sensitive adhesive special for electronic products is characterized in that a formula comprises an alkynyl-containing high-viscosity acrylate copolymer, azide-naphthalene-containing ring-type tetrafunctional epoxy resin and a catalyst.
2. The special high-viscosity high-temperature-resistant pressure-sensitive adhesive for electronic products according to claim 1, which is characterized in that: the mass ratio of the alkynyl-containing high-viscosity acrylate copolymer to the azidonaphthalene-containing ring-type tetrafunctional epoxy resin is 100:0.1-50: 10.
3. The special high-viscosity high-temperature-resistant pressure-sensitive adhesive for electronic products according to claim 1, which is characterized in that: the alkynyl-containing high-viscosity acrylate copolymer is obtained by reacting acrylic acid-2-ethylhexyl ester, butyl acrylate, N-dimethylacrylamide, 2-acrylic acid 2- (2-naphthylthio) ethyl ester, 2-bromoethyl acrylate and propargyl alcohol in a solvent system.
4. The special high-viscosity high-temperature-resistant pressure-sensitive adhesive for electronic products according to claim 3, which is characterized in that: the mass ratio of the used 2-ethylhexyl acrylate, butyl acrylate, N-dimethylacrylamide, 2- (2-naphthylthio) ethyl 2-acrylate, 2-bromoethyl acrylate and propargyl alcohol is (100-) -250): (20-70): (5-50): (5-50): (1-40): (1-50).
5. The special high-viscosity high-temperature-resistant pressure-sensitive adhesive for electronic products according to claim 1, which is characterized in that: the alkynyl-containing high-viscosity acrylate copolymer is synthesized by polymerizing acrylic acid-2-ethylhexyl ester, butyl acrylate, N-dimethylacrylamide, 2-acrylic acid 2- (2-naphthylthio) ethyl ester and 2-bromoethyl acrylate in a solvent system to react A, and then adding propargyl alcohol to react B.
6. The special high-viscosity high-temperature-resistant pressure-sensitive adhesive for electronic products according to claim 1, which is characterized in that: the tetrafunctional epoxy resin containing azide naphthalene ring is obtained by reacting naphthalene ring tetrafunctional epoxy resin, sodium azide and aluminum trichloride in a solvent system.
7. The special high-viscosity high-temperature-resistant pressure-sensitive adhesive for electronic products according to claim 6, wherein the special high-viscosity high-temperature-resistant pressure-sensitive adhesive comprises: the mass ratio of the naphthalene ring type tetrafunctional epoxy resin, the sodium azide and the aluminum trichloride is (30-100): (1-20): (0.1-0.5).
8. The preparation method of the special high-viscosity high-temperature-resistant pressure-sensitive adhesive for the electronic products according to any one of claims 1 to 7, which is characterized in that: and (2) uniformly mixing the alkynyl-containing high-viscosity acrylate copolymer, the azidonaphthalene-containing ring-type tetrafunctional epoxy resin and the catalyst in an inert atmosphere.
9. The high-viscosity high-temperature-resistant pressure-sensitive protective film based on the high-viscosity high-temperature-resistant pressure-sensitive adhesive special for the electronic product, which is disclosed by any one of claims 1 to 7, is characterized in that: the adhesive comprises a 20-75 mu m polyethylene terephthalate release film, a 5-50 mu m pressure-sensitive adhesive layer and a 5-100 mu m polyimide film from bottom to top, wherein the pressure-sensitive adhesive layer is formed by coating the special high-viscosity high-temperature-resistant pressure-sensitive adhesive for the electronic products as claimed in any one of claims 1-7.
10. The preparation method of the high-viscosity high-temperature-resistant pressure-sensitive protective film according to claim 9, which is characterized by comprising the following process steps:
under the protection of nitrogen, the special high-viscosity high-temperature-resistant pressure-sensitive adhesive for the electronic product as described in any one of claims 1 to 7 is coated on a polyimide film, is placed at 80 to 200 ℃ for heat preservation, drying and curing for 5 to 60min to form a pressure-sensitive adhesive layer, a polyethylene terephthalate release film is attached to the front surface of the pressure-sensitive adhesive layer, is placed at 40 to 60 ℃, and is subjected to post-curing for 24 to 100 hours to obtain the high-viscosity high-temperature-resistant pressure-sensitive protective film.
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| WO2006012569A1 (en) * | 2004-07-22 | 2006-02-02 | The Scripps Research Institute | Polymeric materials via click chemistry |
| CN101652405A (en) * | 2006-10-17 | 2010-02-17 | 国家淀粉及化学投资控股公司 | 1 of trinitride and alkynes, the cycloaddition of 3-dipole |
| CN102344524A (en) * | 2011-07-12 | 2012-02-08 | 浙江大学 | Water-soluble click-reaction hyperbranched polymer |
| CN104995229A (en) * | 2013-02-08 | 2015-10-21 | Sika技术股份公司 | Synthesis of polyurethane polymers via copper azide-alkyne click chemistry for coatings, adhesives, sealants and elastomer applications |
| CN107614570A (en) * | 2015-04-24 | 2018-01-19 | 宾州研究基金会 | Click-reaction waterborne polymeric and cross-linking aqueous polymer can be clicked on, can click-reaction functional compounds, click function waterborne polymeric and application thereof |
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Patent Citations (5)
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|---|---|---|---|---|
| WO2006012569A1 (en) * | 2004-07-22 | 2006-02-02 | The Scripps Research Institute | Polymeric materials via click chemistry |
| CN101652405A (en) * | 2006-10-17 | 2010-02-17 | 国家淀粉及化学投资控股公司 | 1 of trinitride and alkynes, the cycloaddition of 3-dipole |
| CN102344524A (en) * | 2011-07-12 | 2012-02-08 | 浙江大学 | Water-soluble click-reaction hyperbranched polymer |
| CN104995229A (en) * | 2013-02-08 | 2015-10-21 | Sika技术股份公司 | Synthesis of polyurethane polymers via copper azide-alkyne click chemistry for coatings, adhesives, sealants and elastomer applications |
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