CN115558456A - OCA optical adhesive, preparation method thereof and OCA optical adhesive film - Google Patents
OCA optical adhesive, preparation method thereof and OCA optical adhesive film Download PDFInfo
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- CN115558456A CN115558456A CN202210250819.8A CN202210250819A CN115558456A CN 115558456 A CN115558456 A CN 115558456A CN 202210250819 A CN202210250819 A CN 202210250819A CN 115558456 A CN115558456 A CN 115558456A
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
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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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
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Abstract
The invention provides an OCA optical adhesive, a preparation method thereof and an OCA optical adhesive film, and relates to the technical field of adhesives. The OCA optical cement provided by the invention comprises the following preparation raw materials in parts by weight: 0 to 30 portions of fluorine-containing acrylate, 0 to 30 portions of bis-acrylate end-capped polydimethylsiloxane, 30 to 60 portions of (methyl) acrylic acid alkyl ester and 0.5 to 1 portion of photoinitiator. The OCA optical adhesive provided by the invention is grafted with the monomer containing the fluorine group and the siloxane bond, and the optical adhesive is converted into a amphiphobic state from a hydrophilic-oleophilic state under the combined action of the fluorine atom and the siloxane bond, so that the OCA optical adhesive has excellent antifouling performance; and due to the strong polarity of fluorine atoms and the stability of silicon-oxygen bonds, the optical adhesive is endowed with good high-temperature and low-temperature resistance. The preparation raw materials adopted by the invention are cheap and easily available, and the production cost can be reduced; the OCA optical cement has high light transmittance and good adhesive property, and is suitable for popularization and application.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to an OCA optical adhesive, a preparation method thereof and an OCA optical adhesive film.
Background
The art works and decorative buildings need a large amount of adhesive in the process of building and assembling, and the requirement on the light transmittance of the adhesive is extremely high in order not to influence the art effect. The light transmittance of most of the existing optical adhesives can reach over 95 percent, and the requirements of the existing optical adhesives on the light transmittance are met. But outdoor art and decorative buildings require the optical cement to have excellent weather resistance in addition to the requirement of light transmittance. Due to the erosion of rainwater, long-time irradiation of sunlight, change of air temperature and attachment of stains, an OCA optical adhesive which has antifouling performance and can resist high and low temperatures is needed.
Solvent-based pressure-sensitive adhesives (PSAs) typically have a low solids content, about 40-55%, and the solution coating process limits the thickness of the effective coating in conventional applications because it is difficult to effectively evaporate all of the solvent from the thick film, thereby limiting the range of applications for solvent-based pressure-sensitive adhesives. Hot melt adhesives are capable of producing thick films, however most hot melt adhesives are made based on rubber and have drawbacks in light transmission properties. With the development of society, the requirement on environmental protection is higher and higher, and the existing solvent-based optical adhesive (including solvent-based pressure-sensitive adhesive and hot melt adhesive) has the defects of high energy consumption, high pollution and the like. Therefore, there is a need for the development of new optical glues. In recent years, UV-curable optical adhesives have rapidly developed and rapidly occupy a large market share, and UV curing means that a photosensitizer in a system forms active free radicals under ultraviolet irradiation with appropriate wavelength and intensity, and the active free radicals further initiate unsaturated monomers to polymerize, crosslink and the like so as to achieve the purpose of curing. The UV curing has the advantages of high curing speed, less pollution, energy conservation, excellent performance of cured products and the like, and is an environment-friendly green curing technology.
Disclosure of Invention
The invention aims to provide an OCA optical adhesive, a preparation method thereof and an OCA optical adhesive film.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an OCA optical adhesive which comprises the following preparation raw materials in parts by weight: 0 to 30 parts of fluorine-containing acrylate, 0 to 30 parts of bis-acrylate-terminated polydimethylsiloxane, 30 to 60 parts of (methyl) acrylic alkyl ester and 0.5 to 1 part of photoinitiator.
Preferably, the alkyl (meth) acrylate includes one or more of methyl acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isoamyl (meth) acrylate, sec-butyl (meth) acrylate, n-butyl (meth) acrylate, isobornyl (meth) acrylate, 2-methylbutyl (meth) acrylate, 4-methyl-2-pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, tert-butyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isopropyl methacrylate, glycidyl methacrylate, and lauryl methacrylate.
The invention provides a preparation method of OCA optical cement in the technical scheme, which comprises the following steps:
and mixing the fluorine-containing acrylate, the dimethacrylate-terminated polydimethylsiloxane, the (methyl) acrylic acid alkyl ester and the photoinitiator to obtain the OCA optical cement.
Preferably, the preparation method of the fluorine-containing acrylate comprises the following steps:
under the protection atmosphere, mixing fluorocarbon alcohol, diisocyanate and a catalyst to perform a first polyaddition reaction to obtain an isocyanate group-terminated fluorine-containing prepolymer;
and mixing the isocyanate-terminated fluorine-containing prepolymer, hydroxyl acrylate and a polymerization inhibitor, and carrying out a second polyaddition reaction to obtain the fluorine-containing acrylate.
Preferably, the fluorocarbon alcohol comprises one or more of trifluoroethanol, pentafluoroethanol, trifluoropropanol, tetrafluoropropanol, hexafluoropropanol, hexafluoroisopropanol, tetrafluorobutanol, hexafluorobutanol, perfluorobutanol, pentafluoropentanol and octafluoropentanol;
the diisocyanate comprises one or more of hexamethylene diisocyanate, isophorone diisocyanate, l, 3-dimethyl isocyanate cyclohexane, l, 4-dimethyl isocyanate cyclohexane, dicyclohexylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate and 4, 4-diphenylmethane diisocyanate;
the hydroxy acrylate includes at least one of hydroxyethyl acrylate, 4-hydroxy-butyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.
Preferably, the molar ratio of the fluorocarbon alcohol to the diisocyanate is 1; the molar ratio of the diisocyanate to the hydroxyl acrylate is 1.
Preferably, the preparation method of the diacrylate-terminated polydimethylsiloxane comprises the following steps:
under the protective atmosphere, mixing dihydroxy-terminated polydimethylsiloxane, diisocyanate and a catalyst, and carrying out a third trimerization addition reaction to obtain an isocyanate-terminated polydimethylsiloxane prepolymer;
and mixing the isocyanate group-terminated polydimethylsiloxane prepolymer, hydroxyl acrylate and a polymerization inhibitor, and carrying out fourth polyaddition reaction to obtain the diacrylate-terminated polydimethylsiloxane.
Preferably, the bishydroxy terminated polydimethylsiloxane comprises bishydroxyethyl terminated polydimethylsiloxane, bishydroxypropyl terminated polydimethylsiloxane or bisamino terminated polydimethylsiloxane.
Preferably, the molar ratio of the bishydroxy-terminated polydimethylsiloxane to the diisocyanate is 100:101 to 200; the molar ratio of the dihydroxy-terminated polydimethylsiloxane to the hydroxy acrylate is 100:2 to 200.
The invention provides an OCA optical adhesive film which is formed by curing the OCA optical adhesive in the technical scheme or the OCA optical adhesive prepared by the preparation method in the technical scheme.
The invention provides an OCA optical adhesive which comprises the following preparation raw materials in parts by weight: 0 to 30 parts of fluorine-containing acrylate, 0 to 30 parts of bis-acrylate-terminated polydimethylsiloxane, 30 to 60 parts of (methyl) acrylic alkyl ester and 0.5 to 1 part of photoinitiator. The OCA optical adhesive provided by the invention is grafted with the monomer containing the fluorine-containing group and the siloxane bond, and the optical adhesive is changed from a hydrophilic-oleophylic state to a amphiphobic state under the combined action of the fluorine atom and the siloxane bond, so that the OCA optical adhesive has excellent antifouling performance; and due to the strong polarity of fluorine atoms and the stability of silicon-oxygen bonds, the optical adhesive is endowed with good high-temperature and low-temperature resistance. The preparation raw materials adopted by the invention are cheap and easily available, and the production cost can be reduced; the OCA optical cement has high light transmittance and good adhesive property, and is suitable for popularization and application.
Detailed Description
The invention provides an OCA optical adhesive which comprises the following preparation raw materials in parts by weight: 0 to 30 portions of fluorine-containing acrylate, 0 to 30 portions of bis-acrylate end-capped polydimethylsiloxane, 30 to 60 portions of (methyl) acrylic acid alkyl ester and 0.5 to 1 portion of photoinitiator.
In the present invention, all the starting materials for the preparation are commercially available products well known to those skilled in the art, unless otherwise specified.
In the invention, the raw materials for preparing the OCA optical cement comprise 0-30 parts by weight of fluorine-containing acrylate, preferably 15-20 parts by weight of fluorine-containing acrylate.
In the invention, the raw materials for preparing the OCA optical adhesive comprise 0-30 parts of bis-acrylate-terminated polydimethylsiloxane, preferably 15-20 parts by weight of the fluorine-containing acrylate.
In the invention, the raw materials for preparing the OCA optical cement comprise 30 to 60 parts of (methyl) acrylic acid alkyl ester, preferably 40 to 50 parts of (methyl) acrylic acid alkyl ester based on the weight part of the fluorine-containing acrylate. In the present invention, the alkyl (meth) acrylate preferably includes one or more of methyl acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isoamyl (meth) acrylate, sec-butyl (meth) acrylate, n-butyl (meth) acrylate, isobornyl (meth) acrylate, 2-methylbutyl (meth) acrylate, 4-methyl-2-pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, t-butyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isopropyl methacrylate, glycidyl methacrylate, and lauryl methacrylate.
In the invention, the raw materials for preparing the OCA optical cement comprise 0.5-1 part of photoinitiator, preferably 0.6-0.8 part of photoinitiator by weight parts of the fluorine-containing acrylate. In the present invention, the photoinitiator is preferably a benzophenone-based cleavage type photoinitiator, more preferably 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone or 4-chlorobenzophenone.
The invention also provides a preparation method of the OCA optical cement, which comprises the following steps:
and mixing the fluorine-containing acrylate, the dimethacrylate-terminated polydimethylsiloxane, the (methyl) acrylic acid alkyl ester and the photoinitiator to obtain the OCA optical cement.
The following will first describe in detail the preparation of fluoroacrylate and bisacrylate end-capped polydimethylsiloxanes.
In the present invention, the method for preparing the fluoroacrylate preferably comprises:
under the protection atmosphere, mixing fluorocarbon alcohol, diisocyanate and a catalyst to perform a first polyaddition reaction to obtain an isocyanate group-terminated fluorine-containing prepolymer;
and mixing the isocyanate-terminated fluorine-containing prepolymer, hydroxyl acrylate and a polymerization inhibitor, and carrying out a second polyaddition reaction to obtain the fluorine-containing acrylate.
In the present invention, preferably, the fluorocarbon alcohol, the diisocyanate and the catalyst are mixed under a protective atmosphere to perform a first polyaddition reaction to obtain an isocyanate group-terminated fluorine-containing prepolymer. In the present invention, the fluorocarbon alcohol preferably includes one or more of trifluoroethanol, pentafluoroethanol, trifluoropropanol, tetrafluoropropanol, hexafluoropropanol, hexafluoroisopropanol, tetrafluorobutanol, hexafluorobutanol, perfluorobutanol, pentafluoropentanol and octafluoropentanol. In the present invention, the diisocyanate preferably includes one or more of hexamethylene diisocyanate, isophorone diisocyanate, l, 3-dimethylisocyanate cyclohexane, l, 4-dimethylisocyanate cyclohexane, dicyclohexylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, and 4, 4-diphenylmethane diisocyanate. In the present invention, the catalyst is preferably an organotin-based catalyst, and more preferably at least one of dibutyltin dilaurate and stannous octoate. In the present invention, the mass of the catalyst is preferably 0.05 to 0.1% of the total mass of the fluorocarbon alcohol and the diisocyanate.
In the present invention, the molar ratio of the fluorocarbon alcohol to the diisocyanate is preferably 1.
In the present invention, the fluorocarbon alcohol, diisocyanate and catalyst mixture preferably comprises: premixing fluorocarbon alcohol and diisocyanate, heating to the temperature of the first polyaddition reaction, and then dropwise adding a catalyst.
In the present invention, the temperature of the first polyaddition reaction is preferably 50 to 90 ℃, more preferably 60 to 80 ℃; the time of the first polyaddition reaction is preferably 1 to 3 hours.
In the present invention, the protective atmosphere is preferably a nitrogen atmosphere.
After the isocyanate group-ended fluorine-containing prepolymer is obtained, in the present invention, the isocyanate group-ended fluorine-containing prepolymer is preferably mixed with a hydroxy acrylate and a polymerization inhibitor to carry out a second polyaddition reaction to obtain a fluorine-containing acrylate. In the present invention, the hydroxy acrylate preferably includes at least one of hydroxyethyl acrylate, 4-hydroxy-butyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate. In the present invention, the molar ratio of the diisocyanate to the hydroxy acrylate is preferably 1. In the present invention, the polymerization inhibitor is preferably one or more of a phenolic polymerization inhibitor and a quinone polymerization inhibitor, and more preferably hydroquinone, t-butylcatechol, p-hydroxyanisole, p-benzoquinone, methylhydroquinone or 2-t-butylhydroquinone. In the present invention, the mass of the polymerization inhibitor is preferably 0.05 to 1% of the total mass of the isocyanate group-ended fluorine-containing prepolymer and the hydroxyl acrylate.
In the present invention, the temperature of the second polyaddition reaction is preferably 50 to 90 ℃, more preferably 60 to 80 ℃; the time of the second polyaddition reaction is preferably 1 to 3 hours.
In the present invention, the preparation method of the bisacrylate-terminated polydimethylsiloxane preferably comprises the following steps:
under the protective atmosphere, mixing dihydroxy-terminated polydimethylsiloxane, diisocyanate and a catalyst, and carrying out a third trimerization addition reaction to obtain an isocyanate-terminated polydimethylsiloxane prepolymer;
and mixing the isocyanate group-terminated polydimethylsiloxane prepolymer, hydroxyl acrylate and a polymerization inhibitor, and carrying out fourth polyaddition reaction to obtain the diacrylate-terminated polydimethylsiloxane.
In the invention, preferably, under the protective atmosphere, the dihydroxy-terminated polydimethylsiloxane, the diisocyanate and the catalyst are mixed to carry out the third trimerization addition reaction to obtain the isocyanate-terminated polydimethylsiloxane prepolymer. In the present invention, the bishydroxy-terminated polydimethylsiloxane preferably includes bishydroxyethyl-terminated polydimethylsiloxane, bishydroxypropyl-terminated polydimethylsiloxane or bisamino-terminated polydimethylsiloxane; the molecular weight of the bishydroxy-terminated polydimethylsiloxane is preferably 500 to 2000. In the present invention, the diisocyanate preferably includes one or more of hexamethylene diisocyanate, isophorone diisocyanate, l, 3-dimethylisocyanate cyclohexane, l, 4-dimethylisocyanate cyclohexane, dicyclohexylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate and 4, 4-diphenylmethane diisocyanate. In the present invention, the catalyst is preferably an organotin-based catalyst, and more preferably at least one of dibutyltin dilaurate and stannous octoate. In the present invention, the mass of the catalyst is preferably 0.05 to 0.1% of the total mass of the bishydroxy-terminated polydimethylsiloxane and the diisocyanate.
In the present invention, the molar ratio of the bishydroxy-terminated polydimethylsiloxane to the diisocyanate is preferably 100:101 to 200, more preferably 100:150 to 180 percent.
In the present invention, the bishydroxy-terminated polydimethylsiloxane, diisocyanate and catalyst mixture preferably includes: and (3) premixing the dihydroxy-terminated polydimethylsiloxane and diisocyanate, heating to the temperature of the third trimerization reaction, and then dropwise adding a catalyst.
In the present invention, the temperature of the third polyaddition reaction is preferably 50 to 90 ℃, more preferably 60 to 80 ℃; the time of the third polyaddition reaction is preferably 1 to 3 hours.
In the present invention, the protective atmosphere is preferably a nitrogen atmosphere.
After the isocyanate group-terminated polydimethylsiloxane prepolymer is obtained, the isocyanate group-terminated polydimethylsiloxane prepolymer, the hydroxyl acrylate and the polymerization inhibitor are preferably mixed to perform a fourth polyaddition reaction, so that the diacrylate-terminated polydimethylsiloxane is obtained. In the present invention, the hydroxy acrylate preferably includes at least one of hydroxyethyl acrylate, 4-hydroxy-butyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate. In the present invention, the molar ratio of the bishydroxy-terminated polydimethylsiloxane to the hydroxy acrylate is preferably 100:2 to 200, more preferably 100:100 to 150. In the present invention, the polymerization inhibitor is preferably one or more of a phenolic polymerization inhibitor and a quinone polymerization inhibitor, and more preferably hydroquinone, t-butylcatechol, p-hydroxyanisole, p-benzoquinone, methylhydroquinone or 2-t-butylhydroquinone. In the present invention, the mass of the polymerization inhibitor is preferably 0.05 to 1% of the total mass of the isocyanate group-terminated polydimethylsiloxane prepolymer and the hydroxyl acrylate.
In the present invention, the temperature of the fourth polyaddition reaction is preferably 50 to 90 ℃, more preferably 60 to 80 ℃; the time of the fourth polyaddition reaction is preferably 1 to 3 hours.
After the polydimethylsiloxane terminated by the fluorine-containing acrylate and the diacrylate is prepared, the invention mixes the fluorine-containing acrylate, the polydimethylsiloxane terminated by the diacrylate, the alkyl (methyl) acrylate and the photoinitiator to obtain the OCA optical cement. In the present invention, the mixing is preferably performed under stirring conditions; the stirring speed is preferably 50-1000 r/min; the stirring time is preferably 30min.
The invention also provides an OCA optical adhesive film which is formed by curing the OCA optical adhesive in the technical scheme or the OCA optical adhesive prepared by the preparation method in the technical scheme. In the invention, the thickness of the OCA optical adhesive film is preferably 50 μm. In the present invention, the curing is preferably uv curing; the energy of the ultraviolet light in the ultraviolet light curing process is preferably 200mJ/cm; the distance between the ultraviolet light and the OCA optical cement is preferably 50mm; the time for the ultraviolet light curing is preferably 10 to 15 seconds.
The OCA optical cement provided by the invention has the advantages of high curing speed and high efficiency, and does not need high-temperature curing.
In a specific embodiment of the present invention, the preparation method of the OCA optical adhesive film comprises: laminating two layers of PET release films on two sides of the OCA optical adhesive by using a laminating machine, and performing ultraviolet irradiation by using a high-pressure mercury lamp to obtain an OCA optical adhesive film; the irradiation height of the ultraviolet rays is 50mm; the light irradiation energy was 200mJ/cm.
The OCA optical adhesive film provided by the invention is a pressure-sensitive adhesive film, has moderate initial adhesion, can not generate displacement during lamination, has a lamination process similar to the existing process, and does not need to add new equipment.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Dehydrating the tetrafluoropropanol at 110 ℃ for 2 hours in vacuum, and cooling to room temperature for later use; weighing 111.16g of isophorone diisocyanate (IPDI) and adding into a four-neck flask with a stirrer, a thermometer, a nitrogen inlet pipe and an exhaust pipe, introducing nitrogen into the four-neck flask, and starting stirring; and then weighing 66g of cooled tetrafluoropropanol, slowly dropwise adding the tetrafluoropropanol into a four-neck flask, adding 0.1g of dibutyltin dilaurate after dropwise adding is finished, heating to 60 ℃, controlling the temperature not to exceed 80 ℃, and reacting for 2 hours to obtain the isocyanate group-terminated fluorine-containing prepolymer.
(2) Adding a mixture of 65.07g of hydroxyethyl methacrylate and 0.3g of p-hydroxyanisole to the isocyanate group-terminated fluorine-containing prepolymer synthesized in step (1) while stirring rapidly; and judging the degree of reaction progress by the existence of the characteristic peak without the isocyanate group in the infrared spectrum in the reaction process, and stopping the reaction after the characteristic peak of the isocyanate group completely disappears to obtain the fluorine-containing acrylate.
(3) Dehydrating dihydroxy-terminated polydimethylsiloxane (Mn = 2000) under vacuum at 110 ℃ for 2 hours, and cooling to room temperature for later use; weighing 88.93g of isophorone diisocyanate (IPDI) and adding into a four-neck flask provided with a stirrer, a thermometer, a nitrogen inlet pipe and an exhaust pipe, introducing nitrogen into the four-neck flask, and starting stirring; then 100g of dehydrated dihydroxy-terminated polydimethylsiloxane (molecular weight is 500) is weighed and slowly dripped into a four-neck flask, 0.1g of dibutyltin dilaurate is added after the dripping is finished, the temperature is raised to 70 ℃, the temperature is controlled not to exceed 80 ℃, and the reaction is carried out for 3 hours, so as to obtain the isocyanate-terminated polydimethylsiloxane prepolymer.
(4) Adding a mixture of 52.06g of hydroxyethyl methacrylate and 0.3g of p-hydroxyanisole to the isocyanate group-terminated polydimethylsiloxane prepolymer synthesized in step (3) while stirring rapidly; and judging the degree of reaction progress by the existence of the characteristic peak without the isocyanate group in the infrared spectrum in the reaction process, and stopping the reaction after the characteristic peak of the isocyanate group completely disappears to obtain the dimethacrylate-terminated polydimethylsiloxane.
(5) 60g of ethyl methacrylate, 30g of fluorine-containing acrylate, 30g of bis-acrylate-terminated polydimethylsiloxane and 2.4g of photoinitiator 1-hydroxycyclohexyl phenyl ketone are weighed, added into a flask, stirred for 30 minutes and uniformly mixed to obtain the OCA optical adhesive.
(6) Attaching two layers of PET release films to two sides of the OCA optical adhesive by using a laminating machine, and then carrying out Ultraviolet (UV) irradiation by using a high-pressure mercury lamp, wherein the irradiation height is 50mm, and the irradiation energy is 200mJ/cm, so as to obtain the OCA optical adhesive film, and the thickness of the OCA optical adhesive film is 50 micrometers.
Example 2
Fluoroacrylate and bisacrylate terminated polydimethylsiloxanes were prepared according to the procedure of example 1.
60g of ethyl methacrylate, 15g of fluoroacrylate, 15g of bisacrylate-terminated polydimethylsiloxane and 1.8g of photoinitiator 1-hydroxycyclohexyl phenyl ketone are weighed, added into a flask, stirred for 30 minutes and uniformly mixed to obtain the OCA optical adhesive.
Attaching two layers of PET release films to two sides of the OCA optical adhesive by using a film laminating machine, and then carrying out Ultraviolet (UV) irradiation by using a high-pressure mercury lamp, wherein the irradiation height is 50mm, and the irradiation energy is 200mJ/cm, so as to obtain the OCA optical adhesive film, and the thickness of the OCA optical adhesive film is 50 micrometers.
Example 3
The bisacrylate terminated polydimethylsiloxane was prepared according to the method of example 1.
60g of ethyl methacrylate, 30g of dimethacrylate-terminated polydimethylsiloxane and 1.8g of photoinitiator 1-hydroxycyclohexyl phenyl ketone are weighed, added into a flask, stirred for 30 minutes and uniformly mixed to obtain the OCA optical cement.
Attaching two layers of PET release films to two sides of the OCA optical adhesive by using a film laminating machine, and then carrying out Ultraviolet (UV) irradiation by using a high-pressure mercury lamp, wherein the irradiation height is 50mm, and the irradiation energy is 200mJ/cm, so as to obtain the OCA optical adhesive film, and the thickness of the OCA optical adhesive film is 50 micrometers.
Example 4
The fluorine-containing acrylate was obtained according to the method of example 1.
And weighing 60g of ethyl methacrylate, 30g of fluorine-containing acrylate and 1.8g of photoinitiator 1-hydroxycyclohexyl phenyl ketone, adding the materials into a flask, stirring for 30 minutes, and uniformly mixing to obtain the OCA optical adhesive.
Attaching two layers of PET release films to two sides of the OCA optical adhesive by using a film laminating machine, and then carrying out Ultraviolet (UV) irradiation by using a high-pressure mercury lamp, wherein the irradiation height is 50mm, and the irradiation energy is 200mJ/cm, so as to obtain the OCA optical adhesive film, and the thickness of the OCA optical adhesive film is 50 micrometers.
Example 5
(1) Dehydrating the tetrafluoropropanol at 110 ℃ for 2 hours in vacuum, and cooling to room temperature for later use; weighing 111.16g of isophorone diisocyanate (IPDI) and adding into a four-neck flask with a stirrer, a thermometer, a nitrogen inlet pipe and an exhaust pipe, introducing nitrogen into the four-neck flask, and starting stirring; and then weighing 66g of cooled tetrafluoropropanol, slowly dropwise adding the tetrafluoropropanol into a four-neck flask, adding 0.1g of dibutyltin dilaurate after dropwise adding is finished, heating to 60 ℃, controlling the temperature not to exceed 80 ℃, and reacting for 2 hours to obtain the isocyanate group-terminated fluorine-containing prepolymer.
(2) Adding a mixture of 65.07g of hydroxyethyl methacrylate and 0.3g of p-hydroxyanisole to the isocyanate group-terminated fluorine-containing prepolymer synthesized in step (1) while stirring rapidly; and judging the degree of reaction progress by the existence of the characteristic peak without the isocyanate group in the infrared spectrum in the reaction process, and stopping the reaction after the characteristic peak of the isocyanate group completely disappears to obtain the fluorine-containing acrylate.
(3) Dehydrating bishydroxy-terminated polydimethylsiloxane (Mn = 2000) at 110 ℃ under vacuum for 2 hours, and cooling to room temperature for further use; weighing 88.93g of isophorone diisocyanate (IPDI) and adding into a four-neck flask provided with a stirrer, a thermometer, a nitrogen inlet pipe and an exhaust pipe, introducing nitrogen into the four-neck flask, and starting stirring; then 200g of dehydrated dihydroxy-terminated polydimethylsiloxane (molecular weight of 1000) is weighed and slowly dripped into a four-neck flask, 0.1g of dibutyltin dilaurate is added after the dripping is finished, the temperature is raised to 70 ℃, the temperature is controlled not to exceed 80 ℃, and the reaction is carried out for 3 hours to obtain the isocyanate-terminated polydimethylsiloxane prepolymer.
(4) Adding a mixture of 52.06g of hydroxyethyl methacrylate and 0.3g of p-hydroxyanisole to the isocyanate group-terminated polydimethylsiloxane prepolymer synthesized in step (3) while stirring rapidly; and judging the degree of reaction progress through the existence of the characteristic peak of the isocyanate group in the infrared spectrum in the reaction process, and stopping the reaction after the characteristic peak of the isocyanate group completely disappears to obtain the dimethacrylate terminated polydimethylsiloxane.
(5) Weighing 30g of ethyl methacrylate, 30g of butyl acrylate, 30g of fluorine-containing acrylate, 30g of bis-acrylate-terminated polydimethylsiloxane and 2.4g of photoinitiator 1-hydroxycyclohexyl phenyl ketone, adding the materials into a flask, stirring for 30 minutes, and uniformly mixing to obtain the OCA optical cement.
(6) Attaching two layers of PET release films to two sides of the OCA optical adhesive by using a laminating machine, and then carrying out Ultraviolet (UV) irradiation by using a high-pressure mercury lamp, wherein the irradiation height is 50mm, and the irradiation energy is 200mJ/cm, so as to obtain the OCA optical adhesive film, and the thickness of the OCA optical adhesive film is 50 micrometers.
Comparative example
(1) And weighing 60g of ethyl methacrylate and 1.2g of photoinitiator 1-hydroxycyclohexyl phenyl ketone, adding the ethyl methacrylate and the photoinitiator into a flask, stirring for 30 minutes, and uniformly mixing to obtain the OCA optical adhesive.
(2) Attaching two layers of PET release films to two sides of the OCA optical adhesive by using a laminating machine, and then carrying out Ultraviolet (UV) irradiation by using a high-pressure mercury lamp, wherein the irradiation height is 50mm, and the irradiation energy is 200mJ/cm, so as to obtain the OCA optical adhesive film, and the thickness of the OCA optical adhesive film is 50 micrometers.
Test example
The performance test of the OCA optical adhesive films prepared in the examples 1-5 and the comparative example is carried out, and the detection results are shown in tables 1-3.
The light transmittance and the haze are measured by using a haze meter, and the detection standard is GB/T2410-2008;
the initial adhesion test uses an initial adhesion tester with the model of CZY-G, and the detection standard is GB/T4852-2002;
the permanent adhesion test uses a permanent adhesion tester with the model of CZY-8S, and the detection standard is GB/T4851-2014;
the 180-degree peeling force test uses a universal tensile machine, and the detection standard is GB/T2790-1995;
the antifouling test is that the contact angle is measured by using deionized water and n-hexadecane through a JC20000D1 contact angle measuring instrument, and the detection standard is GB/T30693-2014;
the high and low temperature resistance test is to carry out 180-degree peel strength test after the OCA optical adhesive film is respectively placed at 80 ℃ and-20 ℃ for 72 h.
TABLE 1 results of optical Properties test of examples 1 to 5 and comparative example
As can be seen from Table 1, the light transmittance of examples 1 and 5 was minimally changed after the high temperature and low temperature treatment, indicating that it has good weather resistance and can be adapted to various extreme environments; this is because polydimethylsiloxane, which has excellent stability of a siloxane bond and strong polarity of a fluorine atom, is introduced into a molecular chain and fluorine atoms are introduced into a branched chain, thereby imparting excellent stability to the optical cement. In examples 2 to 4, the optical properties were slightly lowered at high and low temperatures due to the reduction of the content of the silicon oxide bond and the fluorine atom.
TABLE 2 mechanical Property test results of examples 1 to 5 and comparative example
As can be seen from Table 2, the mechanical properties of the samples are far from each other because the bisacrylate terminated polydimethylsiloxane not only functions as a modifier but also functions as a cross-linking agent, so that the adhesive properties of example 4 and the comparative example are poor due to the absence of the cross-linking agent, and thus the samples cannot be applied. Examples 3, 1, 5 and 2 exhibited a decrease in the tack and peel forces and an increase in the initial tack due to the decrease in the amount of crosslinker (bis-acrylate terminated polydimethylsiloxane) and the difference in the amount of soft and hard monomers. The peel strength of the examples 1, 2, 3 and 5 after high temperature treatment has little change, the slightly larger change of the example 4 may be caused by too small cross-linking density to form a stable network structure, and the largest change of the comparative example shows that the introduction of fluorine atoms and polydimethylsiloxane segments greatly enhances the stability of the optical cement. After low temperature treatment, all samples showed a tendency to increase in peel strength because the temperature was lowered, the movement of the molecular segments was restricted, and thus the peel strength was increased. However, the low temperature makes the colloid brittle and easy to crack, while the introduction of the soft segment polydimethylsiloxane well solves the problem, and the sample added with the dimethacrylate terminated polydimethylsiloxane has small change of the peeling strength at the low temperature.
TABLE 3 antifouling test results of examples 1 to 5 and comparative example
As can be seen from Table 3, the hydrophobic property of the optical cement is improved with the increase of the content of the fluorine-containing monomer and the polydimethylsiloxane in the sample, and the optical cement is converted from a non-hydrophobic state (contact angle of 70 degrees) to a hydrophobic state (contact angle of 127 degrees). As can be seen from the contact angle of the n-hexadecane, the oleophobic property of the optical adhesive is improved along with the increase of the content of the fluorine-containing monomer, and the oleophilic state (the contact angle is less than 10 ℃) is changed into the non-oleophilic state (the contact angle is 70 ℃). And the contact angle of the n-hexadecane hardly changes along with the change of the content of the polydimethylsiloxane, which shows that the contact angle of the polydimethylsiloxane to the n-hexadecane hardly has influence, and the theory is also consistent. The results show that the introduction of the fluorine-containing monomer and the polydimethylsiloxane chain segment into the optical adhesive greatly improves the hydrophobic and oleophobic performances of the optical adhesive and has good antifouling performance.
In conclusion, the OCA optical adhesive with good high and low temperature resistance and antifouling performance is prepared by grafting the fluorine-containing monomer and the polydimethylsiloxane chain segment, and the optical adhesive has high light transmittance (more than 95 percent) and high peel strength (up to 18N 25mm) -1 ) And the initial adhesion is moderate. The OCA optical cement provided by the invention has wide application prospect in outdoor artistic works.
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 (10)
1. The OCA optical cement is characterized by comprising the following preparation raw materials in parts by weight: 0 to 30 parts of fluorine-containing acrylate, 0 to 30 parts of bis-acrylate-terminated polydimethylsiloxane, 30 to 60 parts of (methyl) acrylic alkyl ester and 0.5 to 1 part of photoinitiator.
2. The OCA optical paste of claim 1, wherein the alkyl (meth) acrylate comprises one or more of methyl acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isoamyl (meth) acrylate, sec-butyl (meth) acrylate, n-butyl (meth) acrylate, isobornyl (meth) acrylate, 2-methylbutyl (meth) acrylate, 4-methyl-2-pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, t-butyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isopropyl methacrylate, glycidyl methacrylate, and lauryl methacrylate.
3. The preparation method of the OCA optical cement as claimed in any one of claims 1-2, comprising the following steps:
and mixing the fluorine-containing acrylate, the dimethacrylate-terminated polydimethylsiloxane, the (methyl) acrylic acid alkyl ester and the photoinitiator to obtain the OCA optical cement.
4. The method according to claim 3, wherein the method for producing the fluorine-containing acrylate comprises:
under the protection atmosphere, mixing fluorocarbon alcohol, diisocyanate and a catalyst to perform a first polyaddition reaction to obtain an isocyanate group-terminated fluorine-containing prepolymer;
and mixing the isocyanate-terminated fluorine-containing prepolymer, hydroxyl acrylate and a polymerization inhibitor, and carrying out a second polyaddition reaction to obtain the fluorine-containing acrylate.
5. The preparation method according to claim 4, wherein the fluorocarbon alcohol comprises one or more of trifluoroethanol, pentafluoroethanol, trifluoropropanol, tetrafluoropropanol, hexafluoropropanol, hexafluoroisopropanol, tetrafluorobutanol, hexafluorobutanol, perfluorobutanol, pentafluoropentanol and octafluoropentanol;
the diisocyanate comprises one or more of hexamethylene diisocyanate, isophorone diisocyanate, l, 3-dimethyl isocyanate cyclohexane, l, 4-dimethyl isocyanate cyclohexane, dicyclohexylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate and 4, 4-diphenylmethane diisocyanate;
the hydroxy acrylate includes at least one of hydroxyethyl acrylate, 4-hydroxy-butyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.
6. A preparation method according to claim 4 or 5, characterized in that the molar ratio of fluorocarbon alcohol to diisocyanate is 1; the molar ratio of the diisocyanate to the hydroxyl acrylate is 1.
7. The method of claim 3, wherein the bis-acrylate terminated polydimethylsiloxane is prepared by a method comprising the steps of:
under the protective atmosphere, mixing dihydroxy-terminated polydimethylsiloxane, diisocyanate and a catalyst, and carrying out a third trimerization addition reaction to obtain an isocyanate-terminated polydimethylsiloxane prepolymer;
and mixing the isocyanate group-terminated polydimethylsiloxane prepolymer, hydroxyl acrylate and a polymerization inhibitor, and carrying out fourth polyaddition reaction to obtain the diacrylate-terminated polydimethylsiloxane.
8. The method of claim 7, wherein the bishydroxy terminated polydimethylsiloxane comprises bishydroxy ethyl terminated polydimethylsiloxane, bishydroxy propyl terminated polydimethylsiloxane, or bisamino terminated polydimethylsiloxane.
9. The method according to claim 7 or 8, wherein the molar ratio of the bishydroxy-terminated polydimethylsiloxane to the diisocyanate is 100:101 to 200; the molar ratio of the dihydroxy-terminated polydimethylsiloxane to the hydroxy acrylate is 100:2 to 200.
10. An OCA optical adhesive film, characterized in that the OCA optical adhesive film is formed by curing the OCA optical adhesive of any one of claims 1-2 or the OCA optical adhesive prepared by the preparation method of any one of claims 3-9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011190230A (en) * | 2010-03-17 | 2011-09-29 | Toyo Ink Sc Holdings Co Ltd | Silane compound, pressure-sensitive adhesive, method for producing resin composition for adhesive, and optical pressure-sensitive adhesive film |
| CN103992242A (en) * | 2014-05-17 | 2014-08-20 | 北京航空航天大学 | Fluorinated isocyanate and method for preparing fluorinated isocyanate-acrylate copolymer emulsion |
| CN108753185A (en) * | 2018-06-25 | 2018-11-06 | 苏州凡赛特材料科技有限公司 | High reliability TP with OCA optical adhesive tapes with and preparation method thereof |
| CN113088238A (en) * | 2021-03-15 | 2021-07-09 | 武汉大学 | Preparation method of high-peel-force fast-packaging OCA adhesive for low-surface-energy interface lamination |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011190230A (en) * | 2010-03-17 | 2011-09-29 | Toyo Ink Sc Holdings Co Ltd | Silane compound, pressure-sensitive adhesive, method for producing resin composition for adhesive, and optical pressure-sensitive adhesive film |
| CN103992242A (en) * | 2014-05-17 | 2014-08-20 | 北京航空航天大学 | Fluorinated isocyanate and method for preparing fluorinated isocyanate-acrylate copolymer emulsion |
| CN108753185A (en) * | 2018-06-25 | 2018-11-06 | 苏州凡赛特材料科技有限公司 | High reliability TP with OCA optical adhesive tapes with and preparation method thereof |
| CN113088238A (en) * | 2021-03-15 | 2021-07-09 | 武汉大学 | Preparation method of high-peel-force fast-packaging OCA adhesive for low-surface-energy interface lamination |
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