CN117701196A - Low-modulus acrylic ester adhesive film and preparation method and application thereof - Google Patents
Low-modulus acrylic ester adhesive film and preparation method and application thereof Download PDFInfo
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- CN117701196A CN117701196A CN202311721350.2A CN202311721350A CN117701196A CN 117701196 A CN117701196 A CN 117701196A CN 202311721350 A CN202311721350 A CN 202311721350A CN 117701196 A CN117701196 A CN 117701196A
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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
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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Abstract
The invention provides a low-modulus acrylic ester adhesive film, a preparation method and application thereof, wherein the preparation raw materials of the low-modulus acrylic ester adhesive film comprise the following components in parts by weight: 100 parts of acrylate prepolymer, 0.2-5 parts of macromolecular resin M, 0.1-1 part of macromolecular resin N, 0-1 part of cross-linking agent, 0.01-1 part of first photoinitiator and 0.01-3 parts of coupling agent. The low-modulus acrylic acid ester adhesive film provided by the invention has low storage modulus at the low temperature of-20 ℃, better stripping force on a base material, high creep recovery rate in the temperature range of-20 ℃ to-80 ℃, good cohesive property after high-temperature retention test, and good creep recovery and stress relaxation.
Description
Technical Field
The invention belongs to the technical field of display, and particularly relates to a low-modulus acrylic ester adhesive film, and a preparation method and application thereof.
Background
The application of Optically Clear Adhesive (OCA) in consumer electronics such as smart phones, tablet computers, etc. is increasing. Along with the continuous improvement of requirements of people on screen definition and touch experience, the demand for OCA optical cement is also continuously increasing. Foldable electronic devices gradually flow into the market and are deeply favored by consumers, the foldable electronic devices need to be matched with a foldable display screen, and the display screen needs to be fixed on each component in the structure by using an adhesive, so the development of flexible folding OCAs gradually rises. The flexible folded OCA needs to meet at least the requirement of ensuring that the product will not crease or break under 20 ten thousand folds, while the OCA meets the requirements of modulus stability, good adhesion properties, excellent creep recovery, good stress relaxation rate, etc. at a temperature range of-30 ℃ to 80 ℃.
At present, most of OCAs of flexible folding screens are synthesized by a solution method, the solid content of glue is usually 20-40%, solvents such as ethyl acetate, toluene and the like are used in a large amount in the synthesis process, a heat curing process is usually used, curing time is long, production efficiency is low, energy consumption is high, and environmental protection regulation requirements are not met.
The solvent-free UV method for synthesizing the folding screen OCA is that the acrylic acid monomer mixture is irradiated under ultraviolet light to form a partially polymerized acrylic ester prepolymer, auxiliaries such as a cross-linking agent, a photoinitiator and the like are added into the prepolymer, the mixture is uniformly mixed and defoamed, and the mixture is coated on a polyethylene terephthalate (PET) release film and cured by a UV curing device to form an OCA product. The patent CN111004587a uses acrylate polymer, acrylic modified silicone resin, acrylate monomer and the like to synthesize OCA by photopolymerization, and the acrylic modified silicone resin mentioned in the patent contains phenyl structure, which can increase the heat resistance of the adhesive film, but can reduce the adhesion to the substrate, and the silicone resin containing phenyl structure causes yellowing in appearance after aging, which does not meet the optical performance requirement. Patent CN108064202a uses isooctyl acrylate, hydroxybutyl acrylate, dodecyl acrylate, etc., polymerized to coatable viscosity at low light intensity, and adding a large amount of long side chain alkyl chain monomer can reduce storage modulus at low temperature, but too much addition can reduce adhesion to the substrate.
Therefore, development of a low modulus acrylic adhesive film with low storage modulus requirement (storage modulus less than 150 kpa) at low temperature (-20 ℃) and high creep recovery rate and good adhesion effect is a problem to be solved in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a low-modulus acrylic acid ester adhesive film, a preparation method and application thereof, wherein the low-modulus acrylic acid ester adhesive film has high creep recovery rate, meets the storage modulus requirement and has good bonding effect.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a low-modulus acrylate adhesive film, which is prepared from the following raw materials in parts by weight: 100 parts of acrylate prepolymer, 0.2-5 parts of macromolecular resin M, 0.1-1 part of macromolecular resin N, 0.01-1 part of cross-linking agent, 0.01-1 part of first photoinitiator and 0.01-3 parts of coupling agent.
The weight part of the macromolecular resin M is 0.2-5 parts, for example, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, and specific point values among the above point values are limited in space and for brevity, the present invention is not exhaustive of the specific point values included in the range.
The weight part of the macromolecular resin N is 0.1-1 part, for example, 0.1 part, 0.2 part, 0.5 part, 0.8 part, 1 part, and specific point values among the above point values, which are limited in space and for the sake of brevity, the present invention is not exhaustive.
The cross-linking agent is 0.01-1 part by weight, for example, 0.01 part, 0.1 part, 0.2 part, 0.5 part, 0.8 part, 1 part, and specific point values between the above point values, and the present invention is not intended to be exhaustive of the specific point values included in the range for reasons of brevity and conciseness.
The first photoinitiator may be 0.01 to 1 part by weight, for example, 0.01 part, 0.1 part, 0.2 part, 0.5 part, 0.8 part, 1 part, and specific point values between the above point values, and the present invention is not exhaustive of the specific point values included in the range for the sake of brevity and conciseness.
The coupling agent may be present in an amount of 0.01 to 3 parts by weight, for example, 0.01 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, and specific point values between the above point values, and is limited in scope and for brevity, the present invention is not exhaustive of the specific point values included in the range.
In the present invention, the term "low modulus" means that the adhesive film has a storage modulus of less than 200kPa measured at-20 ℃ using a rotational rheometer, and may be, for example, 200kPa, 150kPa, 120kPa, 100kPa, 90kPa, 80kPa, 50kPa, 30kPa, 10kPa, and specific point values between the above point values, and the present invention is not exhaustive of the specific point values included in the range, limited to the spread and for the sake of brevity.
The macromolecular resin M comprises CH 2 ＝CH 2 COOCH 2 CH 2 NHCOO(CH 2 CH 2 O) m H or CH 2 ＝CH 2 COOCH 2 CH 2 NHCOO(CH 2 CH 2 O) m NHCOCH 2 CH 2 COOCH 2 ＝CH 2 M is 80-140, and may be, for example, 80, 100, 120, 140, and specific point values between the above point values, for the sake of brevity and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values included in the described ranges.
The macromolecular resin N comprises CH 2 ＝CH 2 COO[CH 2 CH＝CHCH 2 CH 2 -CH(CH＝CH 2 )-CH 2 -CH＝CH-CH 2 ] n COOCH 2 ＝CH 2 N is 40-50, and may be, for example, 40, 42, 45, 48, 50, and specific point values between the above point values, limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values encompassed by the described ranges.
Preferably, the weight average molecular weight of the macromolecular resin M is 5000-20000, for example, 5000, 6000, 8000, 10000, 12000, 15000, 18000, 20000, and specific point values among the above point values, and the present invention is not exhaustive of the specific point values included in the range for the sake of brevity and conciseness. Preferably 5000-1300.
The macromolecular resin M can be prepared by mixing isocyanate ethyl Acrylate (AOI) or isocyanatoethyl Methacrylate (MOI), polyether glycol and a catalyst, and reacting under inert gas. The catalyst is used for accelerating the reaction rate in the synthesis process, and comprises any one or a combination of at least two of stannous octoate, dibutyl tin dilaurate, tetra-n-butyl titanate and zirconium n-butoxide, and the adding proportion of the catalyst is preferably 0.15-0.5 percent (relative to the mass of the macromolecular resin).
The AOI or MOI monomer contains NCO groups, can react with hydroxyl groups of polyether glycol under certain conditions, and can obtain macromolecular resins M with different structures by controlling the molar ratio of NCO/OH.
The macromolecular resin M containing single carbon-carbon double bond has low crosslinking degree and good flexibility. The macromolecular resin M having two carbon-carbon double bond functional groups is relatively high in crosslinking degree, and from the viewpoint of increasing creep recovery rate without excessively increasing crosslinking degree, the macromolecular resin M having a single carbon-carbon double bond, that is, the macromolecular resin M has a chemical formula of CH 2 ＝CH 2 COOCH 2 CH 2 NHCOO(CH 2 CH 2 O) m H, the weight average molecular weight of the macromolecular resin M is 5000-20000, more preferably the molecular weight is 5000-13000.
Preferably, the preparation method of the macromolecular resin M comprises the following steps: mixing isocyanate ethyl Acrylate (AOI) or isocyano ethyl Methacrylate (MOI), polyether glycol and a catalyst, and reacting under inert gas to obtain the macromolecular resin M.
Preferably, the temperature of the reaction is 60-100 ℃, further preferably 60-80 ℃. The reaction time is 2-3h.
Preferably, the reaction is carried out under an inert gas.
Preferably, the inert gas comprises any one or a combination of at least two of nitrogen, helium or argon.
By testing the infrared spectrum of the material after the reaction is finished for the presence of 2280cm -1 Absorption peak to judge whether NCO has reactedAll of them.
The macromolecular resin M contains a polyether structure, so that the storage modulus at low temperature can be reduced, the flexibility can be improved, the molecular weight of the macromolecular resin N is larger, the crosslinking density is lower, the elastic recovery effect can be improved by containing polybutadiene groups similar to a rubber structure, but when the adding proportion is too large, the compatibility with a system is poor, the haze of a film is increased, and the film with relatively balanced viscosity and storage modulus can be obtained by matching macromolecular resins with different crosslinking densities.
The low-modulus acrylic adhesive film provided by the invention can contain a cross-linking agent, and the addition of the cross-linking agent can further increase cohesive property and heat resistance. The crosslinking agent is preferably added in a proportion of 0 to 1%, more preferably 0 to 0.5% (relative to the total mass of the low modulus acrylate film).
The low-modulus acrylic adhesive film contains a first photoinitiator, wherein the first photoinitiator comprises 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide or benzoin diethyl ether, and the weight part of the first photoinitiator is 0.01-1 part of the optical adhesive. The optical adhesive also contains a siloxane coupling agent, the addition proportion of the coupling agent is preferably 0.01-1% (relative to the mass of the low-modulus acrylate adhesive film), more preferably 0.01-0.5%, and the coupling agent comprises any one or a combination of at least two of gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane and gamma-aminopropyl triethoxysilane.
Preferably, the macromolecular resin N has a weight average molecular weight of 5000-12000, for example, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, and specific point values among the above point values, which are limited in space and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.
Preferably, the glass transition temperature of the macromolecular resin N is between-20 and-60 ℃, for example, it may be between-20 ℃, -30 ℃, -40 ℃, -50 ℃, -60 ℃, and specific values between the above values, the specific values included in the range not being exhaustive for the sake of brevity and for the sake of brevity. The glass transition temperature is preferably-40 to-60 ℃ from the viewpoint of effectively reducing the low-temperature storage modulus and increasing the film flexibility
Preferably, the crosslinking agent comprises any one or a combination of at least two of 1, 4-butanediol methacrylate, 1, 6-hexanediol diacrylate or trimethylolpropane triacrylate.
Preferably, the preparation raw materials of the acrylate prepolymer comprise the following components in parts by weight: 40-85 parts of isooctyl acrylate, 5-10 parts of butyl acrylate, 5-20 parts of hydroxybutyl acrylate, 1-10 parts of isodecyl acrylate, 0.1-5 parts of cohesive monomer, 0.01-0.5 part of chain transfer agent and 0.01-1 part of second photoinitiator.
The weight parts of the isooctyl acrylate are 40-85 parts, for example, 40 parts, 45 parts, 50 parts, 60 parts, 70 parts, 75 parts, 80 parts, 85 parts, and specific point values among the above point values, and the present invention is not exhaustive of the specific point values included in the range for the sake of brevity and conciseness.
The butyl acrylate may be 5-10 parts by weight, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, and specific point values between the above point values, and the present invention is not exhaustive of the specific point values included in the range for reasons of space and brevity.
The weight parts of the hydroxybutyl acrylate are 5 to 20 parts, for example 5 parts, 6 parts, 8 parts, 10 parts, 15 parts, 18 parts, 20 parts, and specific point values between the above point values, are limited in space and for the sake of brevity, the invention is not exhaustive of the specific point values included in the range.
The isodecyl acrylate may be 1 to 10 parts by weight, for example, 1 part, 2 parts, 5 parts, 8 parts, 10 parts, and specific point values between the above point values, and the invention is not intended to be exhaustive of the specific point values included in the range for reasons of space and brevity.
The cohesive monomer may be present in an amount of 0.1 to 5 parts by weight, for example, 0.1 part, 0.2 part, 0.4 part, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, and specific point values between the above point values, although the present invention is not exhaustive of the specific point values included in the range for reasons of brevity and conciseness. The addition of the cohesive monomer can increase the heat resistance at high temperatures.
The chain transfer agent may be present in an amount of 0.01 to 0.5 parts by weight, for example, 0.01 parts, 0.05 parts, 0.1 parts, 0.2 parts, 0.4 parts, 0.5 parts, and specific point values between the above point values, although the present invention is not limited in this regard and for brevity, the specific point values included in the ranges are not exhaustive.
The second photoinitiator may be present in an amount of 0.01 to 1 part by weight, for example, 0.01 part, 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.8 part, 1 part, and specific point values between the above point values, and is limited in scope and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the cohesive monomer comprises any one or a combination of at least two of isobornyl acrylate, N-vinyl pyrrolidone and acryloylmorpholine.
Preferably, the viscosity of the acrylate prepolymer at 25 ℃ is 2000-6000cps, for example, 2000cps, 2500cps, 3000cps, 3500cps, 4000cps, 4500cps, 5000cps, 5500cps, 6000cps, and specific point values between the above point values, are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the acrylate prepolymer has a prepolymerization of 10 to 25%, for example 10%, 15%, 18%, 20%, 22%, 24%, 25%, and specific point values between the above, although for reasons of length and clarity the invention is not intended to be exhaustive of the specific point values comprised in the range.
The present invention provides an acrylic prepolymer of a specific structure as a "primary glue" wherein isodecyl acrylate has a glass transition temperature T g The polymer has the advantages of lower chain length of the side chain, better hydrophobicity and softness, and can reduce the storage modulus at low temperature and improve the adhesive force to the base material. Wherein the addition of the cohesive monomer improves the heat resistance at high temperatures. The combination of the macromolecular resins M and N can reduce the storage modulus at low temperature (-20 ℃). The flexibility of the adhesive film is improved. Introduction into molecular chainThe macromolecular resin N containing polybutadiene type structure increases creep recovery effect. The storage modulus, creep recovery rate and cohesive force performance are balanced by matching with cross-linking agents with different types and different molecular weights.
Glass transition temperature T of isooctyl acrylate g The ratio of isooctyl acrylate is preferably 60 to 85% (relative to the total mass of the prepolymer), more preferably 60 to 75%, which is low in flexibility and can improve the adhesion to a substrate. Butyl acrylate can increase creep recovery effect, increase cohesive property of the adhesive film, preferably the proportion is 5-10%, hydroxybutyl acrylate can increase cohesive property of the adhesive film, preferably the proportion is 5-15% (relative to the total mass of prepolymer), when the content is less than 5%, cohesive property of the adhesive film is poor, heat resistance is poor, when the content is more than 15%, cohesive strength of the adhesive film is too high, storage modulus at low temperature is increased, and creep recovery rate at low temperature is poor. The isodecyl acrylate contains a long side chain structure, and can obviously reduce the storage modulus at low temperature by matching with isooctyl acrylate and hydroxybutyl acrylate, and when the content exceeds 10%, the adhesive property of the adhesive film to a substrate is obviously reduced.
The addition of the cohesive monomer in the acrylate prepolymer can increase the heat resistance at high temperature, the proportion of the cohesive monomer is preferably 0.1-5 parts, more preferably 0.1-2 parts, when the addition amount is less than 0.1 part, the heat resistance at high temperature is insufficient, when the addition proportion is more than 2 parts, the increase of the storage modulus at low temperature is obvious, and the creep recovery rate is poor.
The chain transfer agent in the acrylate prepolymer controls the reaction process and comprises any one or a combination of at least two of n-dodecyl mercaptan, n-octadecyl mercaptan or pentaerythritol tetra (3-mercaptobutyrate).
The chain transfer agent is more preferably a polyfunctional thiol compound, and the commercially available chain transfer agent may be KarenzMT PE1. The content of the chain transfer agent is preferably 0.01 to 0.1% (relative to the total mass of the acrylate prepolymer), more preferably 0.01 to 0.05%.
The photoinitiator content is usually 0.01-0.5% (relative to the total mass of the acrylate prepolymer), when the photoinitiator content is less than 0.01%, the photoinitiator content is too low, and can not be initiated, and when the photoinitiator content is more than 0.5%, the molecular weight of the acrylate prepolymer is lower under the same illumination intensity, so that the cohesive property of the cured low-modulus acrylate adhesive film is affected. The photoinitiator content is preferably 0.1 to 1% (relative to the total mass of the acrylate prepolymer).
The monomers in the acrylate prepolymer are partially polymerized under certain ultraviolet light intensity, and the polymerization degree can be characterized by a prepolymerization rate (%):
prepolymerization ratio (%) = (M 1 -M 2 )/M 1 *100；
Wherein M is 2 M is the mass of the prepolymer after drying at 150℃for 2h 1 Is the initial acrylate prepolymer mass. Preferably, the acrylate prepolymer has a prepolymerization ratio of 10 to 25%, the acrylate prepolymerization ratio being positively correlated with the viscosity of the prepolymer, the viscosity of the acrylate prepolymer being measured by a viscometer at room temperature of 25 ℃. When the viscosity of the acrylate prepolymer is less than 2000cps, the viscosity of the acrylate prepolymer is too thin and the cohesive property of the cured film is insufficient. When the viscosity of the acrylate prepolymer is higher than 6000cps, the viscosity of the acrylate prepolymer is too thick to be coated. The invention controls the polymerization reaction by controlling the pre-polymerization rate and the viscosity of the acrylate prepolymer, and controls the initial temperature T of the reaction under the intensity of ultraviolet irradiation 1 (DEGC) and temperature T after completion of the polymerization 2 Controlling the reaction at a temperature of T 2 -T 1 The reaction temperature difference can be 20-60 ℃, and the initial reaction temperature T 1 Can be 25℃at room temperature, and the temperature difference is preferably 20 to 40℃and when the temperature difference is within this range, an acrylic prepolymer having a viscosity of 2000 to 6000cps can be obtained.
Preferably, the preparation method of the acrylate prepolymer comprises the following steps: and (3) reacting isooctyl acrylate, butyl acrylate, hydroxybutyl acrylate, isodecyl acrylate, a cohesive monomer, a chain transfer agent and a second photoinitiator to obtain the acrylate prepolymer.
Preferably, the reaction is carried out under ultraviolet irradiation.
Preferably, the wavelength of the ultraviolet radiation is 280-420nm, for example, 280nm, 300nm, 320nm, 350nm, 380nm, 400nm, 420nm, and specific point values between the above point values, which are limited in space and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.
Preferably, the intensity of the ultraviolet irradiation is 1-20mW/cm 2 For example, it may be 1mW/cm 2 、5mW/cm 2 、10mW/cm 2 、15mW/cm 2 、20mW/cm 2 And the particular values between the above-mentioned values, are limited in space and for brevity, the invention is not intended to exhaustively enumerate the specific values included in the range.
In a second aspect, the present invention provides a method for preparing the low modulus acrylate adhesive film according to the first aspect, the method comprising:
and mixing the acrylate prepolymer, the macromolecular resin M, the macromolecular resin N, the cross-linking agent, the first photoinitiator and the coupling agent, and then curing to obtain the low-modulus acrylate adhesive film.
Preferably, the acrylate prepolymer, the macromolecular resin M, the macromolecular resin N, the crosslinking agent, the first photoinitiator and the coupling agent are mixed, coated on a release film, and cured to obtain the low-modulus acrylate adhesive film.
Preferably, the release film comprises a polyethylene terephthalate release film.
Preferably, the curing comprises curing under ultraviolet light.
Preferably, the intensity of the ultraviolet irradiation is 1-50mW/cm 2 For example, it may be 1mW/cm 2 、5mW/cm 2 、10mW/cm 2 、15mW/cm 2 、20mW/cm 2 、30mW/cm 2 、40mW/cm 2 、45mW/cm 2 、50mW/cm 2 And the particular values between the above-mentioned values, are limited in space and for brevity, the invention is not intended to exhaustively enumerate the specific values included in the range.
Preferably, the total energy of the radiation of the curing is 3000-6000mJ, for example 3000mJ, 3500mJ, 4000mJ, 4500mJ, 5000mJ, 6000mJ, and specific point values between the above point values, which are not exhaustive in the present invention for the sake of brevity and conciseness.
In a third aspect, the present invention provides an application of the low modulus acrylate adhesive film according to the first aspect in a smart phone, a tablet computer, a smart watch, a media player or a television.
Compared with the prior art, the invention has the following beneficial effects:
the low-modulus acrylate adhesive film provided by the invention has the advantages of good peeling force, low storage modulus at low temperature, good creep recovery rate at low temperature of-20 ℃ and 60 ℃, good cohesive property, good creep recovery and stress relaxation property, good cohesiveness with a substrate, storage modulus at-20 ℃ of 113-147kPa, storage modulus at 25 ℃ of 23-36kPa, storage modulus at 60 ℃ of 16-21kPa, normal temperature peeling force of 690-850gf/25mm for a steel plate of 20min, creep recovery rate at-20 ℃ of more than 80%, creep recovery rate at 60 ℃ of more than 75%, load of 1kg at high temperature of 85 ℃, time of more than 166h and sliding distance of less than 0.5mm.
Drawings
FIG. 1 is a GPC chart of a macromolecular resin M provided in preparation example 1 of the present invention;
FIG. 2 is a GPC chart of a macromolecular resin M provided in preparation example 2 of the present invention;
FIG. 3 is a GPC chart of an acrylic prepolymer provided in preparation example 5 of the present invention;
FIG. 4 is a temperature sweep storage modulus plot of the low modulus acrylate adhesive film provided in example 2 of the present invention;
FIG. 5 is a graph showing creep and recovery at 25℃and 60℃of the low modulus acrylate adhesive film provided in example 3 of the present invention;
fig. 6 is a stress-strain diagram of the low modulus acrylate adhesive film provided in example 3 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The experimental materials used in the examples and comparative examples of the present invention are as follows:
EHA, isooctyl acrylate (immortalized chemical industry);
BA, butyl acrylate (immortalized chemical);
IBOA, isobornyl acrylate (changxing chemical);
HBA, hydroxybutyl acrylate (osaka organic chemistry);
ACMO, acryloylmorpholine (immortalized chemical);
NVP, N-vinylpyrrolidone (immortalized chemical);
IDA, isodecyl acrylate (changxing chemical); the method comprises the steps of carrying out a first treatment on the surface of the
HDDA,1, 6-hexanediol diacrylate (immortalized chemical);
KBM-403, silicone coupling agent (Xinyue chemical);
a photoinitiator 651, benzil dimethyl ether, (IGM company);
AOI, isocyanate ethyl acrylate (japan sho, inc);
dibutyl tin laurate catalyst (commercially available);
a photoinitiator TPO, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide (IGM company);
DP-6000E, molecular weight 6000 polyether polyol (national chemical industry);
PPG-4000, molecular weight 4000 polyether polyol (national chemical);
PE-1, chain transfer agent (Japanese Showa);
macromolecular resin N: brand BAC-45, acrylate oligomer, M w About 10000, and the functionality is 2.
Preparation example 1
The preparation example provides a macromolecular resin M, wherein the macromolecular resin M contains single carbon-carbon double bonds, and the preparation raw materials of the single-molecule resin M comprise 300 parts of DP-6000E, 0.6 part of dibutyl tin laurate catalyst and 7.1 parts of isocyanate ethyl acrylate.
The preparation method of the macromolecular resin M comprises the following steps: into a 1L three-necked flask was chargedAdding a certain amount of DP-6000E (average molecular weight is 6000 and functionality is 2), heating to 120 ℃ in an oil bath in nitrogen atmosphere, drying for 2-3h, stabilizing the temperature at 75 ℃, adding a certain amount of dibutyl tin laurate catalyst, adding ethyl isocyanate Acrylate (AOI) monomer dropwise by using a dropping funnel for 0.5h, reacting for 4h at 75 ℃ to obtain the macromolecular resin M, weighing part of sample test infrared spectrum during the reaction, and measuring 2280cm -1 No obvious absorption peak of NCO.
The Mw of the macromolecular resin M was about 9300 as measured by Waters GPC, the polydispersity was 1.05, and the GPC spectrum of the macromolecular resin M is shown in FIG. 1, wherein Mn is the number average molecular weight, mw is the weight average molecular weight, mp is the peak molecular weight, mz is the Z average molecular weight, and Mz+1 is the Z+1 average molecular weight.
Preparation example 2
The preparation example provides a macromolecular resin M, wherein the macromolecular resin M contains two carbon-carbon double bonds, and the preparation raw materials of the single-molecule resin M comprise 200 parts of PPG4000, 0.5 part of dibutyl tin laurate catalyst and 7.1 parts of isocyanate ethyl acrylate.
The preparation method of the macromolecular resin M comprises the following steps: adding a certain amount of PPG4000 (average molecular weight is 4000, functionality is 2) into a 1L three-neck flask, heating to 120 ℃ in an oil bath kettle in a nitrogen atmosphere, drying for 2-3 hours, stabilizing the temperature at 75 ℃, adding a certain amount of dibutyl tin laurate catalyst, adding ethyl isocyanate Acrylate (AOI) monomer dropwise by using a dropping funnel for 0.5 hour, then reacting for 4 hours at 75 ℃ to obtain the macromolecular resin M, weighing part of sample test infrared spectrum during the reaction, and measuring 2280cm -1 No obvious absorption peak of NCO.
Testing M of macromolecular resin M by GPC w About 7678, a polydispersity of 1.04. The GPC spectrum of the macromolecular resin M is shown in FIG. 2, wherein Mn is a number average molecular weight, mw is a weight average molecular weight, mp is a peak molecular weight, mz is a Z average molecular weight, and Mz+1 is a Z+1 average molecular weight.
Preparation example 3
The preparation example provides an acrylic acid prepolymer, wherein the preparation raw materials of the acrylic acid prepolymer comprise: 69.5 parts of EHA, 10 parts of BA, 14 parts of HBA, 6 parts of IDA, 0.5 part of IBOA, 0.05 part of 651 initiator, and 0.03 part of PE-1 chain transfer agent.
The preparation method of the acrylic acid prepolymer comprises the following steps: adding EHA, BA, HBA, IDA, IBOA, 651 initiator and PE-1 chain transfer agent into 500mL four-neck flask, introducing nitrogen for 20min, stirring, irradiating for 4min under LED ultraviolet lamp irradiation, and introducing air to inhibit polymerization, wherein the ultraviolet lamp irradiation intensity is 10mw/cm 2 The acrylic acid prepolymer is obtained, the temperature difference before and after the reaction is 25 ℃, the viscosity is 2100cps at 25 ℃, and the prepolymerization rate is about 18%.
Preparation example 4
The preparation example provides an acrylic acid prepolymer, and the preparation raw materials of the acrylic acid prepolymer comprise 65.5 parts of EHA, 10 parts of BA, 14 parts of HBA, 10 parts of IDA, 0.5 part of ACMO, 0.05 part of 651 initiator and 0.03 part of PE-1 chain transfer agent.
The preparation method of the acrylic acid prepolymer comprises the following steps: adding EHA, BA, HBA, IDA, ACMO, 651 initiator and PE-1 chain transfer agent into 500mL four-neck flask, introducing nitrogen for 20min, stirring, irradiating with LED ultraviolet lamp for 3min, and introducing air to inhibit polymerization, wherein the ultraviolet lamp has an intensity of 10mw/cm 2 The acrylic acid prepolymer is obtained, the temperature difference before and after the reaction is 28 ℃, the viscosity is 2861cps at 25 ℃, and the prepolymerization rate is about 22%.
Preparation example 5
The preparation example provides an acrylic acid prepolymer, and the preparation raw materials of the acrylic acid prepolymer comprise 65.3 parts of EHA, 10 parts of BA, 14 parts of HBA, 10 parts of IDA, 0.4 part of NVP, 0.3 part of IBOA, 0.08 part of 651 initiator and 0.03 part of PE-1 chain transfer agent.
The preparation method of the acrylic acid prepolymer comprises the following steps: adding EHA, BA, HBA, IDA, NVP, IBOA, 651 initiator and PE-1 chain transfer agent into 500mL four-neck flask, introducing nitrogen for 20min, stirring, irradiating for 6min under LED ultraviolet lamp irradiation, and introducing air to inhibit polymerization, wherein the ultraviolet lamp irradiation intensity is 10mw/cm 2 The acrylic acid prepolymer is obtained, the temperature difference before and after the reaction is 35 ℃, the viscosity is 4500cps at 25 ℃, and the prepolymer is preparedThe polymerization rate was about 26%. GPC spectra of acrylic prepolymers are shown in FIG. 3, wherein Mn is the number average molecular weight, mw is the weight average molecular weight, mp is the peak molecular weight, mz is the Z average molecular weight, and Mz+1 is the Z+1 average molecular weight.
Example 1
The embodiment provides a low-modulus acrylic acid ester adhesive film and a preparation method thereof, wherein the low-modulus acrylic acid ester adhesive film comprises the following components in parts by weight: 100 parts of acrylic acid ester prepolymer (preparation example 3), 3 parts of macromolecular resin M (preparation example 1), 0.2 part of macromolecular resin N, 0.5 part of TPO and 0.3 part of KBM-403.
The preparation method comprises the following steps: weighing acrylate prepolymer, adding macromolecular resin M and macromolecular resin N, TPO, KBM-403, mixing uniformly, standing for defoaming, coating on a 50um PET transparent release film, covering a layer of 50um transparent PET release film on the upper layer, and curing under an LED ultraviolet lamp with curing power of 20mw/cm 2 And curing the low-modulus acrylate adhesive film with total energy of 4000 mJ.
The components of examples 1 to 6 and comparative examples 1 to 6 are shown in tables 1 and 2, and the preparation method is the same as that of example 1.
TABLE 1
TABLE 2
The low modulus acrylate films provided in examples 1-6 and comparative examples 1-6 were tested for performance by the following procedure:
(1) 180℃peel strength test (unit N/25 mm): with reference to GB/T2792-1998, the test substrate is a 50um PET film and the test glue thickness is 50um;
temperature sweep of shear modulus: the low-modulus acrylic adhesive film with the thickness of 50-200um is stacked into a plurality of layers, and a cylinder with the diameter of 800-1000um is punched out and is taken as a sample. The sample is placed between probes of a rheometer. The temperature scan was performed by rising from-30 ℃ to 100 ℃ at 5 ℃/min. During this rise, the sample oscillates at a frequency of 1Hz and a shear strain of 0.1%. Recording the shear storage modulus (G') at the selected critical temperature;
(3) High temperature holding force test: preparing a low-modulus acrylic adhesive film into a sample with the size of 25mm or 150mm (the back of the double-sided adhesive tape needs to be stuck with 25-mu PET as a backing), testing a SUS304 mirror plate of a plate, after sticking, rolling by a 2kg press roller back and forth for 3 times, hanging weight for 20min, and obtaining the qualified product, wherein the displacement is less than or equal to 1.0mm after 80 ℃/166 h;
(4) Creep recovery test: the low-modulus acrylic adhesive film with the thickness of 50-200um is stacked into a plurality of layers, and a cylinder with the diameter of 800-1000um is punched out and is taken as a sample. Placing the sample between probes of a rheometer, applying a shear stress of 10kpa by using the rheometer, and recovering for 600s;
(5) Static folding test: a 100 μm thick layer (X) of adhesive composition was laminated between two 50 μm Polyimide (PI) sheets to form a PI/X/PI sandwich construction, and then cut to dimensions of 25.4mm width by 125mm length. The samples were then placed in two flat plate holders with a bend radius of 3mm or 5mm at-20℃for 24h. After 24 hours, the sample was removed from the fixture from the-20 ℃ environment and the observed sample passed the static hold test if no buckling or delamination of the composite structure was exhibited;
(6) Stress relaxation: the low-modulus acrylic adhesive film with the thickness of 50-200um is stacked into a plurality of layers, and a cylinder with the diameter of 800-1000um is punched out and is taken as a sample. The sample is placed between probes of a rheometer. By applying 400% strain, the application time was 10min, the relaxation time was 10min, and the stress values before and after the end of the test.
The low modulus acrylate films provided in examples 1-6 and comparative examples 1-6 were subjected to performance tests, and the test results are shown in tables 3 and 4.
TABLE 3 Table 3
TABLE 4 Table 4
The temperature-scanned storage modulus graph of the low-modulus acrylate adhesive film provided in example 2 is shown in fig. 4, the creep and recovery graphs at 25 ℃ and 60 ℃ of the low-modulus acrylate adhesive film provided in example 3 are shown in fig. 5, and the stress-strain graph of the low-modulus acrylate adhesive film provided in example 3 is shown in fig. 6.
From the data in tables 3 to 4, it is clear that the adhesive films with better overall properties can be obtained by using the macromolecular resin M and the macromolecular resin N in combination, and in examples 1 to 3, the normal temperature peeling force of the cohesive monomers IBOA and NVP monomer used in combination is higher, and the creep recovery rate is better. In examples 4 and 5, the creep recovery rate was reduced by using the macromolecular resin N having a relatively low molecular weight. The HDDA crosslinking agent used in comparative examples 1 to 3 has a low molecular weight and a high crosslinking density, resulting in a decrease in peel force. In comparative examples 4 to 6, macromolecular resins N having different molecular weights were used in combination, and the crosslinking density was high and the peeling force was remarkably reduced.
The applicant states that the present invention is illustrated by the above examples as a low modulus acrylate adhesive film and a method of making and using the same, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The low-modulus acrylic acid ester adhesive film is characterized by comprising the following preparation raw materials in parts by weight: 100 parts of acrylate prepolymer, 0.2-5 parts of macromolecular resin M, 0.1-1 part of macromolecular resin N, 0.01-1 part of cross-linking agent, 0.01-1 part of first photoinitiator and 0.01-3 parts of coupling agent;
the macromolecular resin M comprises CH 2 ＝CH 2 COOCH 2 CH 2 NHCOO(CH 2 CH 2 O) m H or CH 2 ＝CH 2 COOCH 2 CH 2 NHCOO(CH 2 CH 2 O) m NHCOCH 2 CH 2 COOCH 2 ＝CH 2 M is 80-140;
the macromolecular resin N comprises CH 2 ＝CH 2 COO[CH 2 CH＝CHCH 2 CH 2 -CH(CH＝CH 2 )-CH 2 -CH＝CH-CH 2 ] n COOCH 2 ＝CH 2 The value of n is 40-50.
2. The low modulus acrylate adhesive film according to claim 1, wherein said macromolecular resin M has a weight average molecular weight of 5000-20000, preferably 5000-13000.
3. The low modulus acrylate adhesive film according to claim 1 or 2, wherein said macromolecular resin N has a weight average molecular weight of 5000-12000;
preferably, the glass transition temperature of the macromolecular resin N is-40 to-60 ℃.
4. The low modulus acrylate film according to any one of claims 1 to 3 wherein said crosslinking agent comprises any one or a combination of at least two of 1, 4-butanediol methyl diacrylate, 1, 6-hexanediol diacrylate or trimethylolpropane triacrylate.
5. The low modulus acrylate adhesive film according to any one of claims 1 to 4, wherein said acrylate prepolymer is prepared from the following raw materials in parts by weight: 40-85 parts of isooctyl acrylate, 5-10 parts of butyl acrylate, 5-20 parts of hydroxybutyl acrylate, 1-10 parts of isodecyl acrylate, 0.1-5 parts of cohesive monomer, 0.01-0.5 part of chain transfer agent and 0.01-1 part of second photoinitiator;
preferably, the cohesive monomer comprises any one or a combination of at least two of isobornyl acrylate, N-vinyl pyrrolidone and acryloylmorpholine.
6. The low modulus acrylate adhesive film according to any one of claims 1 to 5, wherein said acrylate prepolymer has a viscosity of 2000 to 6000cps at 25 ℃;
preferably, the acrylate prepolymer has a prepolymerization of 10 to 25%.
7. The low modulus acrylate film according to any one of claims 1 to 6, wherein said acrylate prepolymer is prepared by a process comprising: reacting isooctyl acrylate, butyl acrylate, hydroxybutyl acrylate, isodecyl acrylate, a cohesive monomer, a chain transfer agent and a second photoinitiator to obtain the acrylate prepolymer;
preferably, the reaction is carried out under ultraviolet irradiation;
preferably, the wavelength of the ultraviolet irradiation is 280-420nm;
preferably, the intensity of the ultraviolet irradiation is 1-20mW/cm 2 。
8. A method of preparing the low modulus acrylate film according to any one of claims 1 to 7 comprising:
and mixing the acrylate prepolymer, the macromolecular resin M, the macromolecular resin N, the cross-linking agent, the first photoinitiator and the coupling agent, and then curing to obtain the low-modulus acrylate adhesive film.
9. The preparation method of claim 8, wherein the acrylate prepolymer, the macromolecular resin M, the macromolecular resin N, the crosslinking agent, the first photoinitiator and the coupling agent are mixed, coated on a release film, and cured to obtain the low-modulus acrylate adhesive film;
preferably, the release film comprises a polyethylene terephthalate release film;
preferably, the curing comprises curing under ultraviolet light;
preferably, the intensity of the light of the curing is 1-50mW/cm 2 ；
Preferably, the total energy of the radiation of the curing is 3000-6000mJ.
10. Use of the low modulus acrylate film according to any of claims 1-7 in a smart phone, tablet, smart watch, media player or television.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119161820A (en) * | 2024-10-18 | 2024-12-20 | 广东皇冠新材料科技有限公司 | Bending resistant optical adhesive sheet |
| CN119371908A (en) * | 2024-12-24 | 2025-01-28 | 博益鑫成高分子材料股份有限公司 | A kind of bending-resistant acrylic film and its preparation method and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119161820A (en) * | 2024-10-18 | 2024-12-20 | 广东皇冠新材料科技有限公司 | Bending resistant optical adhesive sheet |
| CN119371908A (en) * | 2024-12-24 | 2025-01-28 | 博益鑫成高分子材料股份有限公司 | A kind of bending-resistant acrylic film and its preparation method and application |
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