WO2021103680A1 - 一种液态光学透明胶及其制备方法 - Google Patents

一种液态光学透明胶及其制备方法 Download PDF

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Publication number
WO2021103680A1
WO2021103680A1 PCT/CN2020/110713 CN2020110713W WO2021103680A1 WO 2021103680 A1 WO2021103680 A1 WO 2021103680A1 CN 2020110713 W CN2020110713 W CN 2020110713W WO 2021103680 A1 WO2021103680 A1 WO 2021103680A1
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Prior art keywords
optical transparent
liquid optical
monomer
acrylate
transparent glue
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PCT/CN2020/110713
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English (en)
French (fr)
Inventor
金燕兵
胡勇
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上海金門量子科技有限公司
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Publication of WO2021103680A1 publication Critical patent/WO2021103680A1/zh

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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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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

Definitions

  • the present invention relates to the technical field of adhesives, and more specifically, the present invention relates to a liquid optical transparent glue and a preparation method thereof.
  • Optical transparent adhesive is usually made of optical acrylic adhesive without a substrate, and then a layer of release film is attached to the upper and lower bottom layers to form a double-sided adhesive tape without a substrate.
  • the color is transparent, the transmittance is above 90%, the bonding strength is good, it can be cured at room temperature or medium temperature, and it has the characteristics of small curing shrinkage.
  • Liquid optical transparent glue is divided into two categories, one is resistive and the other is capacitive.
  • the resistive optical glue can be divided into 50 ⁇ m and 25 ⁇ m according to the thickness.
  • the capacitive optical glue is divided into 100 ⁇ M. 175 ⁇ M, 200 ⁇ M, 250 ⁇ M.
  • Optical transparent glue can be used in different fields, such as electronics or electrical fields, according to its thickness.
  • optical transparent glue for touch screens, especially the bonding of display panels, display panels, and flexible display screens is an important development direction at present, which can make the surface-to-surface bonding with higher strength, avoid Newton’s rings, and make the product The surface is flatter and the boundary is enlarged.
  • the liquid optical transparent glue used for bonding each panel of the touch screen includes acrylic, silicone, unsaturated polyester, epoxy, etc., among which the most widely used is the acrylic liquid optical transparent glue, which has good toughness and Light transmittance, but it will be damaged after many times of bending, and the bonding performance and chromaticity are poor.
  • CN1490371A reported an adhesive for optical parts, which is composed of (a) (meth)acrylic acid alkyl ester, (b) hydroxyl-containing monomer, (c) containing any one of carboxyl group, amide group, and amino group.
  • the copolymer obtained from a functional monomer is composed of a polyol modified xylylene diisocyanate crosslinking agent and the like.
  • the resulting adhesive has the characteristics of high transparency, good weather resistance, and is not easy to turn yellow over time.
  • CN106795405A provides an optically transparent adhesive through an acrylic monomer mixture, including a polymer containing an acrylic monomer composition, the acrylic monomer composition containing a hydroxyl-containing monomer and a monofunctional (methyl) ) Alkyl acrylate has an excellent balance of adhesive strength and cohesive strength, and a high dielectric constant with excellent optical properties.
  • CN1884415A, CN101208403A provide an antistatic acrylic transparent adhesive, which is obtained by using an acrylic copolymer (A), an ionic compound (B), and a curing agent (C) having a hydroxyl group and an alkylene oxide chain on the side chain.
  • Conductive anti-static adhesive with excellent transparency, almost no coloring, excellent peelability, less static peeling during peeling, etc., suitable for surface protection and bonding of various displays, polarizers and other optical components .
  • the current optical transparent glue has good transparency and toughness, it often has the problem of decreased adhesion under repeated bending or movement, and it cannot achieve the balance of adhesion and toughness.
  • the maximum strain, resilience and storage modulus need to be further improved.
  • the first aspect of the present invention provides a liquid optical transparent glue.
  • the raw materials for preparing the liquid optical transparent glue include 45 to 55 parts of prepolymer and 6 to 12 parts of reactive diluent in parts by weight. And 1 to 1.5 parts of photoinitiator.
  • the raw materials for the preparation of the prepolymer include acrylate monomers and functional monomers, and the acrylate monomers include hard monomers and soft monomers in a weight ratio of (2 ⁇ 3). ): (2 ⁇ 3).
  • the functional monomer accounts for 0.01-5 wt% of the acrylate monomer, and the functional monomer includes a chain transfer agent and a crosslinking monomer.
  • the weight ratio of the monomers is (0.5-1):1.
  • the preparation method of the prepolymer includes the following steps:
  • the functional monomer further includes acrylamide and hydroxy acrylate, and the weight ratio of the acrylamide, hydroxy acrylate and chain transfer agent is (1-2): (1-2) ): (0.01 ⁇ 0.2).
  • the reactive diluent includes a monofunctional reactive diluent and a bifunctional reactive diluent, and the weight ratio is (6-10):1.
  • the monofunctional reactive diluent is selected from at least two of alicyclic alcohol acrylate, alkyl alcohol acrylate or aryl alcohol acrylate.
  • the bifunctional reactive diluent includes hexanediol diacrylate and neopentyl glycol polymethyl oxirane diacrylate, and the weight ratio is (2 to 3): 1.
  • the second aspect of the present invention provides a method for preparing the above-mentioned liquid optical transparent glue, which includes the following steps:
  • the raw materials for preparing the liquid optical transparent glue are mixed to obtain the liquid optical transparent glue.
  • the third aspect of the present invention provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • the fourth aspect of the present invention provides an application of the above-mentioned liquid optical transparent glue, which is applied in the electronic or electrical field.
  • the present invention provides a liquid optical transparent glue, which can improve the cohesive strength and bonding strength by controlling the preparation method and preparation raw materials of the prepolymer, thereby improving the liquid optical transparency
  • the toughness of the glue and the peel strength after multiple bendings, and it has good chroma in addition, by controlling the type of active diluent, the toughness of the prepared liquid optical transparent glue can be further increased, so that when tens of thousands of bendings occur There will be no glass, blistering, folding, etc., and it has good bonding performance. It still has good bonding power after multiple bending, and has good cohesive strength, maximum strain and resilience. It can be used For electronics or electricity, it is especially suitable for touch screens, especially the bonding of display panels, display screens, and display flexible screens.
  • compositions, step, method, product, or device containing the listed elements is not necessarily limited to those elements, but may include other elements not explicitly listed or inherent in such a composition, step, method, product, or device Elements.
  • the first aspect of the present invention provides a liquid optical transparent glue.
  • the raw materials for preparing the liquid optical transparent glue include 45 to 55 parts by weight of prepolymer, 6 to 12 parts of reactive diluent, and 1 to 1.5 parts by weight. Photoinitiator.
  • the raw materials for preparing the liquid optical transparent glue of the present invention include 50 parts of prepolymer, 9 parts of active diluent and 1.2 parts of photoinitiator.
  • Prepolymer is the most basic raw material in UV curing adhesives, and its molecular weight and molecular weight distribution have a greater impact on the bonding performance of the adhesive; and the composition and chemical structure of the prepolymer, as well as the composition and structure of the synthetic prepolymer raw material The optical properties of sensitive adhesives have a greater impact.
  • the raw materials for preparing the prepolymer of the present invention include acrylate monomers and functional monomers.
  • the acrylate monomers include hard monomers and soft monomers, and the weight ratio is (2 to 3) : (2 ⁇ 3); further, the weight ratio of the hard monomer and the soft monomer of the present invention is 1:1.
  • hard monomers include, but are not limited to, methyl methacrylate, acrylic acid, isobornyl methacrylate, ethyl methacrylate, vinyl acetate, 3-hydroxy-1-adamantyl methacrylate .
  • soft monomers include, but are not limited to, ethyl acrylate, butyl acrylate, n-octyl acrylate, isooctyl acrylate, isooctyl methacrylate, dodecyl methacrylate, 2-ethyl acrylate ⁇ hexyl ester.
  • the hard monomer of the present invention is methyl methacrylate and acrylic acid, and the weight ratio is 1: (0.1-0.2); further, the weight ratio of methyl methacrylate and acrylic acid is 1: 0.13.
  • the soft monomer of the present invention is 2-ethylhexyl acrylate and butyl acrylate, and the weight ratio is (1-2): (1-2); further, the acrylic acid-2 of the present invention -The weight ratio of ethylhexyl ester and butyl acrylate is 1:1.
  • the functional monomer of the present invention accounts for 0.01 to 5 wt% of the acrylate monomer, and the functional monomer includes a chain transfer agent and a crosslinking monomer.
  • the weight ratio is (0.5-1):1; further, the functional monomer of the present invention accounts for 4.05% by weight of the acrylate monomer, and the functional monomer includes a chain transfer agent and a crosslinking monomer.
  • the weight ratio of chain transfer agent and crosslinking monomer is 0.8:1.
  • the chain transfer agent is a substance that can effectively transfer the chain growth free radicals to adjust the relative molecular mass of the polymer.
  • the present invention does not specifically limit the chain transfer agent. Examples include isopropanol, sodium formate, dodecyl mercaptan, octadecyl mercaptan, 2-cyanopropyl-2-ylbenzodisulfide and mercapto group. Ethanol; In one embodiment, the chain transfer agent of the present invention is dodecyl mercaptan.
  • Crosslinking monomers are monomers with two or more functional groups.
  • the present invention does not specifically limit the crosslinking monomers. Examples include tripropylene glycol diacrylate, hexanediol diacrylate, and dipropylene glycol. Diacrylate;
  • the crosslinking monomer of the present invention is tripropylene glycol diacrylate.
  • the preparation method of the prepolymer of the present invention includes the following steps:
  • the solvent is a well-known solvent to those skilled in the art, and examples include ethyl acetate, ethanol and acetone.
  • the solvent of the present invention is ethyl acetate.
  • Initiator is a kind of compound that is easily decomposed into free radicals (ie primary free radicals) by heat. It can be used to initiate the free radical polymerization and copolymerization of vinyl and diene monomers, and can also be used for crosslinking of unsaturated polyesters. Curing and polymer cross-linking reaction.
  • the initiator of the present invention is a well-known initiator to those skilled in the art, including triethylamine (TEA), 1,4-diazabicyclo[2.2.2]octane (DABCO), dilauric acid Butyl tin (DBTDL), stannous octoate (SO), dibenzoyl peroxide (BPO); in a preferred embodiment, the catalyst of the present invention is dibenzoyl peroxide.
  • TAA triethylamine
  • DBTDL 1,4-diazabicyclo[2.2.2]octane
  • DBTDL dilauric acid Butyl tin
  • SO stannous octoate
  • BPO dibenzoyl peroxide
  • the initiator of the present invention accounts for 0.4 to 0.6 wt% of the acrylate monomer.
  • the polymerization end point of the prepolymer is determined by the determination of iodine value.
  • the specific method is to measure the iodine value every 0.5h after the hard monomer and soft monomer are added dropwise. When the iodine value becomes stable, the polymerization inhibitor is added The reaction is stopped and the prepolymer is obtained.
  • Polymerization inhibitor is an industrial auxiliary, usually used to prevent the progress of polymerization. Inhibitor molecules react with chain free radicals to form non-radical substances or low-activity free radicals that cannot be initiated, thereby terminating the polymerization.
  • the polymerization inhibitor of the present invention is a polymerization inhibitor well known to those skilled in the art, and is not specifically limited. Examples include hydroquinone, p-benzoquinone, methylhydroquinone, p-hydroxyanisole, 2- Tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone.
  • the applicant controlled the reaction time to 0.5-0.6h and added a chain transfer agent to avoid disproportionation and the formation of unstable agents. End groups to control the molecular weight of the final prepolymer.
  • the applicant found that by using the prepolymer preparation method of the present invention to prepare a core-shell prepolymer, the stability of the reaction can be promoted, and the Improve the bonding strength, but the applicant found that due to the influence of the prepared prepolymer shell and core structure, it will have an impact on the transmittance chromaticity of the prepared optical transparent glue.
  • the functional monomer of the present invention further includes acrylamide and hydroxy acrylate, and the weight ratio of acrylamide, hydroxy acrylate and chain transfer agent is (1 ⁇ 2): (1 ⁇ 2): (0.01-0.2); further, the weight ratio of acrylamide, hydroxyacrylate and chain transfer agent of the present invention is 2:2:0.02.
  • acrylamide examples include, but are not limited to, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-(butyl) (Meth)acrylamide, N-tert-butyl(meth)acrylamide, N-pentyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-heptyl(meth)acrylamide , N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, piperidinyl (meth)acrylamide, morpholinyl (meth)acrylamide.
  • hydroxy acrylates include, but are not limited to, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 3-hydroxy-1-adamantyl methacrylate ( CAS number: 115372-36-6), caprolactone acrylate.
  • the acrylamide of the present invention is N-methyl(meth)acrylamide.
  • the hydroxy acrylate of the present invention is caprolactone acrylate.
  • Caprolactone acrylate is a comonomer formed by the joint action of caprolactone and acrylic acid, and both ends contain hydroxyl and double bonds; the caprolactone acrylate of the present invention is purchased from Dow, USA, and the brand is TONE M-100 .
  • acrylamide and hydroxyacrylate are added to react to obtain the prepolymer.
  • the optical clear adhesive has multiple bending
  • the toughness and peel strength during folding are significantly improved, and the chromaticity of the optical clear adhesive can also be improved. This may be because the functional monomer is added at the end during the preparation of the prepolymer, so that the functional monomer is polymerized in the prepolymer.
  • the end of the body core-shell structure, and the amide functional group and the hydroxyl functional group contained in the functional monomer can increase the adhesion of the optical clear adhesive to the substrate through hydrogen bonding, van der Waals force, etc., and the increase in the intermolecular force is also conducive to internal
  • the increase of the poly strength increases the peel strength of the optical clear adhesive.
  • the hydroxyl acrylates, especially the caprolactone acrylates can undergo cross-linking reaction, which can promote the further increase of the viscosity of the prepolymer, thereby promoting the prepolymerization.
  • the growth of the body chain makes the molecular weight of the final prepared prepolymer between 8000 and 15000, so that the prepolymer has suitable cohesive strength and increases the cohesiveness during multiple bending.
  • the long-chain caprolactone enters the main chain of the prepolymer, which is also conducive to the increase in toughness.
  • the applicant has discovered that when the selected hard monomers, soft monomers, and functional monomers have a large difference in activity, a homopolymer of a certain more reactive monomer may be formed, while a monomer with a lower activity may be formed. Will not participate in the reaction, so the present invention selects hard monomers, soft monomers and functional monomers with suitable activity through multiple experiments, and a copolymerization reaction occurs, thereby forming the prepolymer of the present invention containing a variety of different monomer structures .
  • Reactive diluent is a kind of low-molecular compound used to reduce the viscosity of the system. It is used to reduce the viscosity of the system, improve the fluidity, wettability, and permeability, and is convenient for coating.
  • the prepolymer used in UV-curable adhesives is in a viscous liquid state, and a certain amount of diluent is added to adjust the viscosity of the system.
  • the reactive diluent of the present invention includes a monofunctional reactive diluent and a bifunctional reactive diluent, and the weight ratio is (6-10):1; further, the monofunctional reactive diluent of the present invention The weight ratio of reactive diluent and bifunctional reactive diluent is 8:1.
  • the functionality is the number of functional groups in a molecule of monomer that can participate in the reaction in the condensation reaction.
  • the monofunctional reactive diluent of the present invention is selected from at least two of alicyclic alcohol acrylate, alkyl alcohol acrylate or aryl alcohol acrylate.
  • alicyclic alcohol acrylates include, but are not limited to, isobornyl methacrylate and isobornyl acrylate.
  • alkyl alcohol acrylates include, but are not limited to, butyl acrylate, isooctyl acrylate, methyl methacrylate, acrylic acid, ethyl methacrylate, ethyl acrylate, butyl acrylate, n-octyl acrylate, Isooctyl methacrylate, dodecyl methacrylate, 2-ethylhexyl acrylate.
  • aryl alcohol acrylates include, but are not limited to, 2-phenoxyethyl acrylate.
  • the monofunctional reactive diluent of the present invention includes alicyclic alcohol acrylate and alkyl alcohol acrylate, and the weight ratio is (1-2): (1-2); further, the lipid of the present invention The weight ratio of cyclic alcohol acrylate and alkyl alcohol acrylate is 1:1.
  • the alicyclic alcohol acrylate of the present invention is a C4-C10 alicyclic alcohol acrylate; further, the alicyclic alcohol acrylate of the present invention is selected from butyl acrylate and isooctyl propylene octanoate, and the weight ratio is (2 to 4): 1; further, the weight ratio of the alicyclic alcohol acrylate of the present invention selected from butyl acrylate and isooctyl propionate is 3:1.
  • the alicyclic alcohol acrylate of the present invention is isobornyl methacrylate.
  • the bifunctional reactive diluent of the present invention includes hexanediol diacrylate and neopentyl glycol polymethyl oxirane diacrylate, and the weight ratio is (2 ⁇ 3) :1; Further, the weight ratio of the hexanediol diacrylate and the neopentyl glycol polymethyl oxirane diacrylate of the present invention is 2:1.
  • Neopentyl glycol polymethyl oxirane diacrylate (CAS number: 84170-74-1) is propoxylated neopentyl glycol diacrylate with good diluting properties and low viscosity.
  • the prepolymer of the present invention has a relatively high molecular weight and viscosity.
  • the prepolymer is diluted by adding a reactive diluent to reduce the viscosity of the prepolymer and promote the uniform dispersion of the prepolymer and the reactive diluent.
  • a reactive diluent to reduce the viscosity of the prepolymer and promote the uniform dispersion of the prepolymer and the reactive diluent.
  • bifunctional reactive diluents with different chain lengths such as hexanediol diacrylate, neopentyl glycol polymethyl oxide Alkyl diacrylate can form a dense and sparse cross-linked system.
  • the shear force will be affected by the denser cross-linked network formed by hexanediol diacrylate and neopentyl glycol polymethyl epoxy
  • the sparse cross-linked network of ethane diacrylate can be transmitted together, thereby reducing the breakage of the molecular chain of the optical transparent adhesive and increasing the peel strength and flexibility during multiple bending.
  • Photoinitiators are compounds that can absorb a certain wavelength of energy in the ultraviolet light region (250-420nm) or visible light region (400-800nm), generate free radicals, cations, etc., thereby initiating monomer polymerization, crosslinking and curing.
  • the present invention does not specifically limit the photoinitiator.
  • Examples include 2959 photoinitiator, 184 photoinitiator, 1173 photoinitiator, 907 photoinitiator, TPO photoinitiator, TPO-L photoinitiator, IHT-PI 910 photoinitiator, 659 photoinitiator, MBF photoinitiator, IHT-PI 4265 photoinitiator, IHT-PI 1000 photoinitiator, IHT-PI 500 photoinitiator.
  • the photoinitiator of the present invention includes 2959 photoinitiator and 1173 photoinitiator, and the weight ratio is (1 ⁇ 2): (0.3 ⁇ 0.8); further, the 2959 photoinitiator of the present invention And 1173 photoinitiator, the weight ratio is 1.2:0.5.
  • the present invention controls the preparation of prepolymers and the types of active diluents, so as to adjust the glass transition temperature of the liquid optical transparent glue prepared to be between -50°C and -20°C, wherein the glass transition temperature of the present invention is In order to test according to DSC, so as to meet the preparation of solid optical transparent glue, as well as the application in the electronic or electrical field.
  • the second aspect of the present invention provides a method for preparing the liquid optical transparent glue as described above, which includes the following steps:
  • the raw materials for preparing the liquid optical transparent glue are mixed to obtain the liquid optical transparent glue.
  • the third aspect of the present invention provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • the liquid optical clear adhesive (LOCA) is coated on the release film, and an appropriate oven temperature is selected according to the glass transition temperature for drying, and then cured by a UV curing device to obtain the solid optical clear adhesive (OCA) thickness It can be 25-100 ⁇ m, including 25 ⁇ m, 50 ⁇ m, 75 ⁇ m, 100 ⁇ m.
  • the solid optical transparent glue can be combined with PC, CPI (transparent polyimide), PI, PMMA, PET and other materials with a laminating machine.
  • the panel is laminated with good adhesion, toughness, maximum strain and resilience, and has a suitable cohesive strength, and will not peel off, bubbles, and folds for tens of thousands of bending.
  • the fourth aspect of the present invention provides the application of the liquid optical transparent glue as described above, which is applied in the electronic or electrical field.
  • the liquid optical transparent glue of the present invention controls the peeling strength, toughness, viscosity and cohesive strength of the liquid optical transparent glue through the joint action of the raw materials. It can be applied in the electronic or electrical fields, and is especially suitable for the contact between the panels of the touch screen. Lamination.
  • Embodiment 1 of the present invention provides a liquid optical clear glue.
  • the preparation raw materials of the liquid optical clear glue include 55 parts by weight of prepolymer, 12 parts of reactive diluent and 1.5 parts of photoinitiator.
  • the raw materials for the preparation of the prepolymer include acrylate monomers and functional monomers, the acrylate monomers include hard monomers and soft monomers, the weight ratio is 2:3, and the hard monomer is methyl methacrylate.
  • the weight ratio of ester and acrylic acid is 1:0.2
  • the soft monomer is 2-ethylhexyl acrylate and butyl acrylate
  • the weight ratio is 1:2
  • the functional monomer accounts for the proportion of the acrylic ester monomer. 5wt%
  • the functional monomer includes N-methyl(meth)acrylamide, caprolactone acrylate, dodecyl mercaptan and tripropylene glycol diacrylate
  • the weight ratio is 2:2:0.02:0.025 .
  • the preparation method of the prepolymer includes the following steps: adding 15wt% hard monomer, 5wt% soft monomer, tripropylene glycol diacrylate, dodecyl mercaptan and dibenzoyl peroxide into ethyl acetate Mix, react at 75°C for 0.5h, add the remaining hard monomer and soft monomer dropwise, add N-methyl(meth)acrylamide and caprolactone acrylate, reflux, and measure the iodine value every 0.5h. When the value tends to be stable, hydroquinone is added to obtain a prepolymer; the dibenzoyl peroxide accounts for 0.5 wt% of the acrylic monomer.
  • the reactive diluent includes a monofunctional reactive diluent and a bifunctional reactive diluent with a weight ratio of 10:1.
  • the monofunctional reactive diluent includes isobornyl methacrylate and alkyl alcohol acrylate, by weight The ratio is 1:2, the alicyclic alcohol acrylate is selected from the group consisting of butyl acrylate and isooctyl propanoate, and the weight ratio is 4:1.
  • the bifunctional reactive diluent includes hexanediol diacrylate and neopentyl
  • the glycol polymethyl oxirane diacrylate has a weight ratio of 3:1.
  • the photoinitiator includes 2959 photoinitiator and 1173 photoinitiator, and the weight ratio is 1:0.8.
  • This example also provides the method for preparing the liquid optical transparent glue as described above, which includes the following steps:
  • the raw materials for preparing the liquid optical transparent glue are mixed to obtain the liquid optical transparent glue.
  • This example also provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • Embodiment 2 of the present invention provides a liquid optical transparent glue.
  • the raw materials for preparing the liquid optical transparent glue include 45 parts by weight of prepolymer, 6 parts of active diluent and 1 part of photoinitiator.
  • the raw materials for the preparation of the prepolymer include acrylate monomers and functional monomers, the acrylate monomers include hard monomers and soft monomers, with a weight ratio of 3:2, and the hard monomer is methyl methacrylate.
  • the weight ratio of ester and acrylic acid is 1:0.1
  • the soft monomer is 2-ethylhexyl acrylate and butyl acrylate
  • the weight ratio is 2:1.
  • the functional monomer accounts for the proportion of the acrylic ester monomer. 3wt%
  • the functional monomer includes N-methyl(meth)acrylamide, caprolactone acrylate, dodecyl mercaptan and tripropylene glycol diacrylate, and the weight ratio is 1:1:0.01:0.01 .
  • the preparation method of the prepolymer includes the following steps: adding 15wt% hard monomer, 5wt% soft monomer, tripropylene glycol diacrylate, dodecyl mercaptan and dibenzoyl peroxide into ethyl acetate Mix and react at 75°C for 0.5h. After adding the remaining hard monomer and soft monomer dropwise, N-methyl(meth)acrylamide and caprolactone acrylate are refluxed, and the iodine value is measured every 0.5h. When the iodine value is When it becomes stable, hydroquinone is added to obtain a prepolymer; the dibenzoyl peroxide accounts for 0.5 wt% of the acrylic monomer.
  • the reactive diluent includes a monofunctional reactive diluent and a bifunctional reactive diluent with a weight ratio of 6:1, and the monofunctional reactive diluent includes isobornyl methacrylate and alkyl alcohol acrylate, by weight The ratio is 2:1, the alicyclic alcohol acrylate is selected from butyl acrylate and isooctyl propanoate, the weight ratio is 4:1, and the bifunctional reactive diluent includes hexanediol diacrylate and neopentyl
  • the glycol polymethyl oxirane diacrylate has a weight ratio of 3:1.
  • the photoinitiator includes 2959 photoinitiator and 1173 photoinitiator, and the weight ratio is 2:0.3.
  • This example also provides the method for preparing the liquid optical transparent glue as described above, which includes the following steps:
  • the raw materials for preparing the liquid optical transparent glue are mixed to obtain the liquid optical transparent glue.
  • This example also provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • Example 3 of the present invention provides a liquid optical transparent glue.
  • the raw materials for preparing the liquid optical transparent glue include 50 parts by weight of prepolymer, 9 parts of reactive diluent and 1.2 parts of photoinitiator.
  • the raw materials for the preparation of the prepolymer include acrylate monomers and functional monomers, the acrylate monomers include hard monomers and soft monomers, and the weight ratio of hard monomers and soft monomers is 1:1,
  • the hard monomer is methyl methacrylate and acrylic acid, and the weight ratio is 1:0.13.
  • the soft monomer is 2-ethylhexyl acrylate and butyl acrylate, and the weight ratio is 1:1.
  • the monomer accounts for 4.05% by weight of the acrylate monomer
  • the functional monomer includes N-methyl(meth)acrylamide, caprolactone acrylate, dodecyl mercaptan and tripropylene glycol diacrylate ,
  • the weight ratio is 2:2:0.02:0.025.
  • the preparation method of the prepolymer includes the following steps: adding 15wt% hard monomer, 5wt% soft monomer, tripropylene glycol diacrylate, dodecyl mercaptan and dibenzoyl peroxide into ethyl acetate Mix, react at 75°C for 0.5h, add the remaining hard monomer and soft monomer dropwise, add N-methyl(meth)acrylamide and caprolactone acrylate, reflux, and measure the iodine value every 0.5h. When the value tends to be stable, hydroquinone is added to obtain a prepolymer; the dibenzoyl peroxide accounts for 0.5 wt% of the acrylic monomer.
  • the reactive diluent includes a monofunctional reactive diluent and a bifunctional reactive diluent with a weight ratio of 8:1.
  • the monofunctional reactive diluent includes isobornyl methacrylate and alkyl alcohol acrylate, by weight The ratio is 1:1, the alicyclic alcohol acrylate is selected from butyl acrylate and isooctyl propionate, the weight ratio is 3:1, and the bifunctional reactive diluent includes hexanediol diacrylate and neopentyl
  • the glycol polymethyl oxirane diacrylate has a weight ratio of 2:1.
  • the photoinitiator includes 2959 photoinitiator and 1173 photoinitiator, and the weight ratio is 1.2:0.5.
  • This example also provides the method for preparing the liquid optical transparent glue as described above, which includes the following steps:
  • the raw materials for preparing the liquid optical transparent glue are mixed to obtain the liquid optical transparent glue.
  • This example also provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • Embodiment 4 of the present invention provides a liquid optical transparent glue.
  • the raw materials for preparing the liquid optical transparent glue include 50 parts by weight of prepolymer, 9 parts of reactive diluent and 1.2 parts of photoinitiator.
  • the raw materials for the preparation of the prepolymer include acrylate monomers and functional monomers, the acrylate monomers include hard monomers and soft monomers, and the weight ratio of hard monomers and soft monomers is 1:1,
  • the hard monomer is methyl methacrylate and acrylic acid, and the weight ratio is 1:0.13.
  • the soft monomer is 2-ethylhexyl acrylate and butyl acrylate, and the weight ratio is 1:1.
  • the monomer accounts for 0.05% by weight of the acrylate monomer
  • the functional monomer includes dodecyl mercaptan and tripropylene glycol diacrylate in a weight ratio of 0.8:1.
  • the preparation method of the prepolymer includes the following steps: adding 15wt% hard monomer, 5wt% soft monomer tripropylene glycol diacrylate, dodecyl mercaptan and dibenzoyl peroxide into ethyl acetate and mixing , React at 75° C. for 0.5 h, drop the remaining hard monomer and soft monomer, and reflux for 0.5 h to obtain a prepolymer; the dibenzoyl peroxide accounts for 0.5 wt% of the acrylic monomer.
  • the reactive diluent includes a monofunctional reactive diluent and a bifunctional reactive diluent with a weight ratio of 8:1.
  • the monofunctional reactive diluent includes isobornyl methacrylate and alkyl alcohol acrylate, by weight The ratio is 1:1, the alicyclic alcohol acrylate is selected from butyl acrylate and isooctyl propionate, the weight ratio is 3:1, and the bifunctional reactive diluent includes hexanediol diacrylate and neopentyl Glycol polyethylene oxide diacrylate, the weight ratio is 2:1.
  • the photoinitiator includes 2959 photoinitiator and 1173 photoinitiator, and the weight ratio is 1.2:0.5.
  • This example also provides the method for preparing the liquid optical transparent glue as described above, which includes the following steps:
  • the raw materials for preparing the liquid optical transparent glue are mixed to obtain the liquid optical transparent glue.
  • This example also provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • Comparative Example 1 of the present invention provides a liquid optical transparent adhesive.
  • the specific implementation is the same as that of Example 3, except that the acrylic acid is replaced with 3-hydroxy-1-adamantyl methacrylate.
  • This example also provides the method for preparing the liquid optical transparent glue as described above, and the specific implementation is the same as in Example 3.
  • This example also provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • Comparative Example 2 of the present invention provides a liquid optical transparent adhesive.
  • the specific implementation is the same as that of Example 3, except that the butyl acrylate is replaced with dodecyl acrylate.
  • This example also provides the method for preparing the liquid optical transparent glue as described above, and the specific implementation is the same as in Example 3.
  • This example also provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • Comparative Example 3 of the present invention provides a liquid optical transparent adhesive.
  • the specific implementation is the same as that of Example 3. The difference is that the N-methyl (meth)acrylamide is replaced with N-hexyl (meth) propylene. Amide.
  • This example also provides the method for preparing the liquid optical transparent glue as described above, and the specific implementation is the same as in Example 3.
  • Comparative Example 4 of the present invention provides a liquid optical transparent adhesive.
  • the specific implementation is the same as that of Example 3. The difference is that the N-methyl(meth)acrylamide is replaced with N,N-dimethyl( Meth)acrylamide.
  • This example also provides the method for preparing the liquid optical transparent glue as described above, and the specific implementation is the same as in Example 3.
  • This example also provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • Comparative Example 5 of the present invention provides a liquid optical transparent adhesive.
  • the specific implementation is the same as that of Example 3, except that the functional monomer does not include N-methyl(meth)acrylamide.
  • This example also provides the method for preparing the liquid optical transparent glue as described above, and the specific implementation is the same as in Example 3.
  • This example also provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • Comparative Example 6 of the present invention provides a liquid optical transparent adhesive.
  • the specific implementation is the same as that of Example 3, except that the functional monomer does not include caprolactone acrylate.
  • This example also provides the method for preparing the liquid optical transparent glue as described above, and the specific implementation is the same as in Example 3.
  • This example also provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • Comparative Example 7 of the present invention provides a liquid optical transparent adhesive.
  • the specific implementation is the same as that of Example 3, except that the caprolactone acrylate is replaced with 2-hydroxyethyl acrylate.
  • This example also provides the method for preparing the liquid optical transparent glue as described above, and the specific implementation is the same as in Example 3.
  • This example also provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • Comparative Example 8 of the present invention provides a liquid optical transparent glue.
  • the specific implementation is the same as that of Example 3.
  • the difference is that the preparation method of the prepolymer includes the following steps: Dibenzoyl oxide was mixed and reacted at 75°C for 1 hour to obtain a prepolymer.
  • This example also provides the method for preparing the liquid optical transparent glue as described above, and the specific implementation is the same as in Example 3.
  • This example also provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • Comparative Example 9 of the present invention provides a liquid optical transparent adhesive.
  • the specific implementation is the same as that of Example 3.
  • the difference is that the preparation method of the prepolymer includes the following steps: 10wt% hard monomer, 10wt% soft The monomer and dibenzoyl peroxide are mixed, reacted at 75° C. for 0.5 h. After the remaining hard monomer and soft monomer are added dropwise, the functional monomer is added and refluxed for 0.5 h to obtain a prepolymer.
  • This example also provides the method for preparing the liquid optical transparent glue as described above, and the specific implementation is the same as in Example 3.
  • This example also provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • Comparative Example 10 of the present invention provides a liquid optical transparent adhesive.
  • the specific implementation is the same as that of Example 3.
  • the difference is that the bifunctional reactive diluent does not include neopentyl glycol polymethyl ethylene oxide diluent. Acrylate.
  • This example also provides the method for preparing the liquid optical transparent glue as described above, and the specific implementation is the same as in Example 3.
  • This example also provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • Comparative Example 11 of the present invention provides a liquid optical transparent adhesive.
  • the specific implementation is the same as that of Example 3, except that the bifunctional reactive diluent does not include hexanediol diacrylate.
  • This example also provides the method for preparing the liquid optical transparent glue as described above, and the specific implementation is the same as in Example 3.
  • This example also provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • Comparative Example 12 of the present invention provides a liquid optical transparent adhesive.
  • the specific implementation is the same as that of Example 3, except that the neopentyl glycol polymethyl oxirane diacrylate is replaced with tripropylene glycol. Diacrylate.
  • This example also provides the method for preparing the liquid optical transparent glue as described above, and the specific implementation is the same as in Example 3.
  • This example also provides a solid optical transparent glue, which is prepared by coating the above-mentioned liquid optical transparent glue on a release film, drying, and UV curing.
  • Comparative Example 13 of the present invention provides a solid optical clear glue, the brand of the solid optical clear glue is FINESET TE227, and the thickness of the solid optical clear glue is 50 ⁇ m.
  • Static bending test Observe the static bending (outside bending R4/inside bending R2, test environment 60°C, 90% humidity, standing for 240hrs) through the Yuasa bending test machine. ) Whether there are cracks and whitening phenomena afterwards, it is found that the solid optical transparent adhesives provided in Examples 1 to 3 have no cracks and whitening phenomena.
  • Performance test The solid optical transparent adhesives provided in Examples 1 to 3 were tested for optical performance, mechanical properties, and corrosive properties, and found to meet the specifications of solid optical transparent adhesives for touch screens. The performance test methods and standards are shown in Table 2.
  • the liquid optical transparent adhesive provided by the present invention has high toughness, peel strength and chroma, and it has no peeling, bubbles, or folds during dynamic bending more than 200,000 times. After folds 200,000 times, its peel strength is 15N/25mm.
  • the optical clear adhesive provided by Comparative Example 13 has good toughness, its adhesion is weak, especially when it is in motion or when it is flexed multiple times.
  • the liquid optical transparent adhesive provided by the present invention can be used for touch screens, especially display panels, display panels, display flexible screens, and has high strain and resilience, and has suitable cohesive strength.

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Abstract

本发明涉及胶粘剂技术领域，更具体地，本发明涉及一种液态光学透明胶及其制备方法。所述液态光学透明胶的制备原料按重量份计，包括45～55份预聚体、6～12份活性稀释剂和1～1.5份光引发剂。本发明提供一种液态光学透明胶，通过控制预聚体的制备方法和制备原料，以及活性稀释剂的种类，可提高内聚强度和粘结强度，从而提高液态光学透明胶的韧性和多次弯折后的剥离强度，且具有好的色度，使得发生上万次弯折时不会出现玻璃、起泡、翻折等现象，在多次弯折后仍具有好的粘结力，且具有好的内聚强度、最大应变和回弹性，可用于电子或电气，尤其适合于触摸屏，尤其是显示面板、显示屏组、显示柔性屏的粘结。

Description

一种液态光学透明胶及其制备方法 技术领域
本发明涉及胶粘剂技术领域，更具体地，本发明涉及一种液态光学透明胶及其制备方法。
背景技术
光学透明胶(OCA光学胶)通常是将光学亚克力胶做成无基材，然后在上下底层，再各贴合一层离型薄膜，形成一种无基体材料的双面贴合胶带，具有无色透明、透过率在90％以上、胶结强度良好，可在室温或中温下固化，且有固化收缩小等特点。液态光学透明胶分为两大类，一类是电阻式的，一类是电容式的，电阻式的光学胶按厚度不同又可分为50μm和25μm的，电容式的光学胶分为100μM，175μM，200μM，250μM的。光学透明胶按照厚度不同可应用于不同的领域，如电子或电气领域。
光学透明胶用于触摸屏，尤其是显示面板、显示屏组、显示柔性屏的粘结是目前一个重要的发展方向，能够使面与面的粘结有更高的强度，避免牛顿环，使产品表面更加平整，扩大边界。目前用于触摸屏各面板粘结的液态光学透明胶有丙烯酸类，有机硅类，不饱和聚酯类，环氧类等，其中应用最广泛的是丙烯酸类液态光学透明胶，具有好的韧性和透光率，但多次弯折后会出现破损，粘结性能和色度较差。
CN1490371A中报道了一种光学部件用粘合剂，其由(a)(甲基)丙烯酸烷基酯，(b)含羟基的单体，(c)含羧基、酰胺基、氨基中的任意一种官能单体所得到的共聚物与多元醇改性苯二亚甲基二异氰酸酯交联剂等组成。所得胶粘剂具有透明性高，耐候性好，并且随着时间的推移也不容易变黄等特点。
CN106795405A提供了一种光学透明粘合剂，通过丙烯酸磊单体混合物，包括包含丙烯酸类单体组合物的聚合物，所述丙烯酸类单体组合物含有含羟基的单体和单官能(甲基)丙烯酸烷基酯，具有粘合强度和内聚强度的优异平衡以及优异光学特性的高介电常数。
CN1884415A、CN101208403A提供一种防静电丙烯酸类透明胶粘剂，其通过使用包含侧链具有羟基及环氧烷烃链的丙烯酸系共聚物(A)、离子化合物(B)及 固化剂(C)得到的具有适当导电性的防静电粘结剂，具有优良的透明性，几乎不上色，在剥离性优良，剥离时剥离静电少等特点，适用于各种显示器、偏光板等光学构件的表面保护与粘结。
故可知目前的光学透明胶虽然具有好的透明性和韧性，但是在多次弯折或运动状态下往往存在粘结力下降的问题，无法达到粘结力和韧性的平衡，且光学透明胶的最大应变、回弹性和储能模量还需要进一步改善。
发明内容
为了解决上述问题，本发明第一个方面提供了一种液态光学透明胶，所述液态光学透明胶的制备原料按重量份计，包括45～55份预聚体、6～12份活性稀释剂和1～1.5份光引发剂。
作为本发明一种优选的技术方案，所述预聚体的制备原料包括丙烯酸酯单体和功能单体，所述丙烯酸酯单体包括硬单体和软单体，重量比为(2～3)：(2～3)。
作为本发明一种优选的技术方案，所述功能单体占所述丙烯酸酯单体的0.01～5wt％，所述功能单体包括链转移剂和交联单体，所述链转移剂和交联单体的重量比为(0.5～1)：1。
作为本发明一种优选的技术方案，所述预聚体的制备方法包括以下步骤：
将15～20wt％硬单体、5～10wt％软单体、交联单体、链转移剂和引发剂加入溶剂中，在70～80℃反应0.4～0.6h，滴加剩余硬单体和软单体反应，得到预聚体。
作为本发明一种优选的技术方案，所述功能单体还包括丙烯酰胺和羟基丙烯酸酯，所述丙烯酰胺、羟基丙烯酸酯和链转移剂的重量比为(1～2)：(1～2)：(0.01～0.2)。
作为本发明一种优选的技术方案，所述活性稀释剂包括单官能度活性稀释剂和双官能度活性稀释剂，重量比为(6～10)：1。
作为本发明一种优选的技术方案，所述单官能度活性稀释剂选自脂环醇丙烯酸酯、烷基醇丙烯酸酯或芳基醇丙烯酸酯中的至少两种。
作为本发明一种优选的技术方案，所述双官能度活性稀释剂包括己二醇二丙烯酸酯和新戊二醇聚甲基环氧乙烷二丙烯酸酯，重量比为(2～3)：1。
本发明第二个方面提供了一种如上所述的液态光学透明胶的制备方法，包括以下步骤：
将所述液态光学透明胶的制备原料混合，得到所述液态光学透明胶。
本发明第三个方面提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
本发明第四个方面提供了一种如上所述的液态光学透明胶的应用，应用在电子或电气领域。
本发明与现有技术相比具有以下有益效果：本发明提供一种液态光学透明胶，通过控制预聚体的制备方法和制备原料，可提高内聚强度和粘结强度，从而提高液态光学透明胶的韧性和多次弯折后的剥离强度，且具有好的色度；另外通过控制活性稀释剂的种类，可进一步增加制备得到的液态光学透明胶的韧性，使得发生上万次弯折时不会出现玻璃、起泡、翻折等现象，且具有好的粘结性能，在多次弯折后仍具有好的粘结力，且具有好的内聚强度、最大应变和回弹性，可用于电子或电气，尤其适合于触摸屏，尤其是显示面板、显示屏组、显示柔性屏的粘结。
具体实施方式
参选以下本发明的优选实施方法的详述以及包括的实施例可更容易地理解本发明的内容。除非另有限定，本文使用的所有技术以及科学术语具有与本发明所属领域普通技术人员通常理解的相同的含义。当存在矛盾时，以本说明书中的定义为准。
如本文所用术语“由…制备”与“包含”同义。本文中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素，而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。
连接词“由…组成”排除任何未指出的要素、步骤或组分。如果用于权利要求中，此短语将使权利要求为封闭式，使其不包含除那些描述的材料以外的材料，但与其相关的常规杂质除外。当短语“由…组成”出现在权利要求主体的子句中而不是紧接在主题之后时，其仅限定在该子句中描述的要素；其它要素并不被排 除在作为整体的所述权利要求之外。
当量、浓度、或者其它值或参数以范围、优选范围、或一系列上限优选值和下限优选值限定的范围表示时，这应当被理解为具体公开了由任何范围上限或优选值与任何范围下限或优选值的任一配对所形成的所有范围，而不论该范围是否单独公开了。例如，当公开了范围“1至5”时，所描述的范围应被解释为包括范围“1至4”、“1至3”、“1至2”、“1至2和4至5”、“1至3和5”等。当数值范围在本文中被描述时，除非另外说明，否则该范围意图包括其端值和在该范围内的所有整数和分数。
单数形式包括复数讨论对象，除非上下文中另外清楚地指明。“任选的”或者“任意一种”是指其后描述的事项或事件可以发生或不发生，而且该描述包括事件发生的情形和事件不发生的情形。
说明书和权利要求书中的近似用语用来修饰数量，表示本发明并不限定于该具体数量，还包括与该数量接近的可接受的而不会导致相关基本功能的改变的修正的部分。相应的，用“大约”、“约”等修饰一个数值，意为本发明不限于该精确数值。在某些例子中，近似用语可能对应于测量数值的仪器的精度。在本申请说明书和权利要求书中，范围限定可以组合和/或互换，如果没有另外说明这些范围包括其间所含有的所有子范围。
此外，本发明要素或组分前的不定冠词“一种”和“一个”对要素或组分的数量要求(即出现次数)无限制性。因此“一个”或“一种”应被解读为包括一个或至少一个，并且单数形式的要素或组分也包括复数形式，除非所述数量明显旨指单数形式。
以下通过具体实施方式说明本发明，但不局限于以下给出的具体实施例。
本发明第一个方面提供了一种液态光学透明胶，所述液态光学透明胶的制备原料按重量份计，包括45～55份预聚体、6～12份活性稀释剂和1～1.5份光引发剂。
在一种优选的实施方式中，本发明所述液态光学透明胶的制备原料按重量份计，包括50份预聚体、9份活性稀释剂和1.2份光引发剂。
预聚体
预聚体是紫外固化胶中最基本的原料，其分子量大小和分子量分布对胶粘剂的粘结性能影响较大；且预聚体组成成分、化学结构以及合成预聚体原料的组成、结构对压敏胶光学性能影响较大。
在一种实施方式中，本发明所述预聚体的制备原料包括丙烯酸酯单体和功能单体，所述丙烯酸酯单体包括硬单体和软单体，重量比为(2～3)：(2～3)；进一步地，本发明所述硬单体和软单体的重量比为1：1。
作为硬单体的实例，包括但不限于，甲基丙烯酸甲酯、丙烯酸、甲基丙烯酸异冰片酯、甲基丙烯酸乙酯、醋酸乙烯酯、3-羟基-1-金刚烷基甲基丙烯酸酯。
作为软单体的实例，包括但不限于，丙烯酸乙酯、丙烯酸丁酯、丙烯酸正辛酯、丙烯酸异辛酯、甲基丙烯酸异辛酯、甲基丙烯酸十二烷酯、丙烯酸-2-乙基己酯。
优选地，本发明所述硬单体为甲基丙烯酸甲酯和丙烯酸，重量比为1：(0.1～0.2)；进一步地，本发明所述甲基丙烯酸甲酯和丙烯酸的重量比为1：0.13。
更优选地，本发明所述软单体为丙烯酸-2-乙基己酯和丙烯酸丁酯，重量比为(1～2)：(1～2)；进一步地，本发明所述丙烯酸-2-乙基己酯和丙烯酸丁酯的重量比为1：1。
进一步优选地，本发明所述功能单体占所述丙烯酸酯单体的0.01～5wt％，所述功能单体包括链转移剂和交联单体，所述链转移剂和交联单体的重量比为(0.5～1)：1；进一步地，本发明所述功能单体占所述丙烯酸酯单体的4.05wt％，所述功能单体包括链转移剂和交联单体，所述链转移剂和交联单体的重量比为0.8：1。
链转移剂是能有效地使链增长自由基发生自由基转移的物质，用以调节聚合物的相对分子质量。本发明不对链转移剂做具体限定，可列举的有，异丙醇、甲酸钠、十二烷基硫醇、十八烷基硫醇、2-氰丙基-2-基苯并二硫和巯基乙醇；在一种实施方式中，本发明所述链转移剂为十二烷基硫醇。
交联单体是具有两个或两个以上官能团的单体，本发明不对交联单体做具体限定，可列举的有，二缩三丙二醇二丙烯酸酯、己二醇二丙烯酸酯、二丙二醇二丙烯酸酯；在一种优选的实施方式中，本发明所述交联单体为二缩三丙二醇二丙烯酸酯。
优选地，本发明所述预聚体的制备方法包括以下步骤：
将15～20wt％硬单体、5～10wt％软单体、交联单体、链转移剂和引发剂加入溶剂中，在70～80℃反应0.4～0.6h，滴加剩余硬单体和软单体反应，得到预聚体。
所述溶剂为本领域技术人员熟知的溶剂，可列举的有，乙酸乙酯、乙醇、丙酮。在一种实施方式中，本发明所述溶剂为乙酸乙酯。
引发剂为一类容易受热分解成自由基(即初级自由基)的化合物，可用于引发烯类、双烯类单体的自由基聚合和共聚合反应，也可用于不饱和聚酯的交联固化和高分子交联反应。本发明所述引发剂为本领域技术人员熟知的引发剂，可列举的有三乙胺(TEA)、1,4-二氮杂二环[2.2.2]辛烷(DABCO)、二月桂酸二丁基锡(DBTDL)、辛酸亚锡(SO)、过氧化二苯甲酰(BPO)；在一种优选的实施方式中，本发明所述催化剂为过氧化二苯甲酰。本发明所述引发剂占所述丙烯酸酯单体的0.4～0.6wt％。
本发明通过碘值测定来判断预聚体的聚合终点，具体方式为将硬单体和软单体滴加完毕后，每隔0.5h测定碘值，当碘值趋于稳定时加入阻聚剂停止反应，得到预聚体。
阻聚剂是一种工业助剂，通常用于防止聚合作用的进行。阻聚剂分子与链自由基反应，形成非自由基物质或不能引发的低活性自由基，从而使聚合终止。本发明所述阻聚剂为本领域技术人员熟知的阻聚剂，不做具体限定，可列举的有，对苯二酚、对苯醌、甲基氢醌、对羟基苯甲醚、2-叔丁基对苯二酚、2,5-二叔丁基对苯二酚。
申请人发现，通过加入15～20wt％硬单体、5～10wt％硬单体发生热聚合，由于添加的硬单体量较多，如甲基丙烯酸酯和丙烯酸，生成黏稠状物质，相当于形成了比较稳定的核心，并控制反应时间在0.5～0.6h，从而控制分子量在2000～3000，之后滴加剩余丙烯酸酯单体和功能单体时，相当于在核心上接枝聚合物的壳层，形成类似的核壳结构，且由于添加较多的软单体，如丙烯酸-2-乙基己酯和丙烯酸丁酯，导致形成的壳体上有较多的长链侧基，有利于浸润基材，提高其韧性和粘结性；且通过添加丙烯酸，由于丙烯酸带有双键和羧基两个反应基团，使得丙烯酸酯单体发生部分交联，从而导致预聚体的粘度增加，且随着粘度增加， 链增长过程中的自动加速效应延长，促进壳层的生长，申请人通过控制反应时间为0.5～0.6h，并添加链转移剂，避免发生岐化终止形成不稳定剂的端基，从而控制最终形成的预聚体的分子量，申请人发现，通过使用本发明所述预聚体的制备方法，制备得到核壳结构的预聚体，可促进反应的稳定性，还能够提高粘结强度，但是申请人发现，由于制备得到的预聚体壳核结构的影响，会对制备得到的光学透明胶的透光色度产生影响。
在一种优选的实施方式中，本发明所述功能单体还包括丙烯酰胺和羟基丙烯酸酯，所述丙烯酰胺、羟基丙烯酸酯和链转移剂的重量比为(1～2)：(1～2)：(0.01～0.2)；进一步地，本发明所述丙烯酰胺、羟基丙烯酸酯和链转移剂的重量比为2：2：0.02。
作为丙烯酰胺的实例，包括但不限于，N-甲基(甲基)丙烯酰胺、N-乙基(甲基)丙烯酰胺、N-丙基(甲基)丙烯酰胺、N-(丁基)(甲基)丙烯酰胺、N-叔丁基(甲基)丙烯酰胺、N-戊基(甲基)丙烯酰胺、N-己基(甲基)丙烯酰胺、N-庚基(甲基)丙烯酰胺、N,N-二甲基(甲基)丙烯酰胺、N,N-二乙基(甲基)丙烯酰胺、哌啶基(甲基)丙烯酰胺、吗啉基(甲基)丙烯酰胺。
作为羟基丙烯酸酯的实例，包括但不限于，丙烯酸-2-羟乙基酯、甲基丙烯酸羟乙酯、4-羟基丁基丙烯酸酯、3-羟基-1-金刚烷基甲基丙烯酸酯(CAS号：115372-36-6)、己内酯丙烯酸酯。
在一种更优选的实施方式中，本发明所述丙烯酰胺为N-甲基(甲基)丙烯酰胺。
在一种进一步优选的实施方式中，本发明所述羟基丙烯酸酯为己内酯丙烯酸酯。
己内酯丙烯酸酯是己内酯与丙烯酸共同作用而成的共聚单体，两端分别含有羟基和双键；本发明所述己内酯丙烯酸酯购自美国陶氏，牌号为TONE M-100。
在一种进一步优选的实施方式中，本发明所述预聚体的制备方法中，滴加剩余硬单体和软单体后，加入丙烯酰胺和羟基丙烯酸酯反应，得到预聚体。
申请人意外发现，通过添加丙烯酰胺和羟基丙烯酸酯作为功能单体，尤其是N-甲基(甲基)丙烯酰胺和己内酯丙烯酸酯作为功能单体时，所述光学透明胶的多次弯折时的韧性和剥离强度显著提高，也可改善光学透明胶的色度，这可能是因为，通过在预聚体的制备过程中，最后添加功能单体，从而使得功能单体聚合在 预聚体核壳结构的末端，而功能单体中含有的酰胺官能团和羟基官能团可通过氢键、范德华力等增加光学透明胶和基材的粘附作用，且分子间作用力的增加也有利于内聚强度的增加，从而增加光学透明胶的剥离强度，另外，由于羟基丙烯酸酯，尤其是己内酯丙烯酸酯中羟基可以发生交联反应，可促进预聚体粘度的进一步增加，从而促进预聚体链增长的进行，从而使得最后制备得到的预聚体的分子量在8000～15000，使得预聚体具有合适的内聚强度，多次弯折时的粘结性增加。另外，由于己内酯丙烯酸酯中羟基和双键参与反应，使得长链的己内酯进入预聚体主链上，从而也有利于韧性的增加。
另外，申请人发现，当选择的硬单体、软单体、和功能单体的活性相差较大时，可能会生成某种活性较大单体的均聚物，而活性较低的单体不会参与反应，故本发明通过多次试验，选择活性合适的硬单体、软单体和功能单体，发生共聚反应，从而生成本发明所述含有多种不同单体结构的预聚体。
活性稀释剂
活性稀释剂是一类用来降低体系粘度的低分子化合物，用于降低体系黏度，提高流动性、湿润性、渗透性，便于涂布。一般紫外固化胶粘剂中所用的预聚体是呈粘稠的液体状态，加入一定量的稀释剂来调节体系的粘度。
在一种实施方式中，本发明所述活性稀释剂包括单官能度活性稀释剂和双官能度活性稀释剂，重量比为(6～10)：1；进一步地，本发明所述单官能度活性稀释剂和双官能度活性稀释剂的重量比为8：1。
官能度为缩合反应中，一分子单体中能参与反应的官能团数目。
优选地，本发明所述单官能度活性稀释剂选自脂环醇丙烯酸酯、烷基醇丙烯酸酯或芳基醇丙烯酸酯中的至少两种。
作为脂环醇丙烯酸酯的实例，包括但不限于，甲基丙烯酸异冰片酯、丙烯酸异冰片酯。
作为烷基醇丙烯酸酯的实例，包括但不限于，丙烯酸丁酯、丙烯酸异辛酯、甲基丙烯酸甲酯、丙烯酸、甲基丙烯酸乙酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸正辛酯、甲基丙烯酸异辛酯、甲基丙烯酸十二烷酯、丙烯酸-2-乙基己酯。
作为芳基醇丙烯酸酯的实例，包括但不限于，丙烯酸2-苯氧基乙基酯。
更优选地，本发明所述单官能度活性稀释剂包括脂环醇丙烯酸酯和烷基醇丙烯酸酯，重量比为(1～2)：(1～2)；进一步地，本发明所述脂环醇丙烯酸酯和烷基醇丙烯酸酯的重量比为1：1。
进一步优选地，本发明所述脂环醇丙烯酸酯为C4～C10脂环醇丙烯酸酯；进一步地，本发明所述脂环醇丙烯酸酯选自丙烯酸丁酯和丙辛酸异辛酯，重量比为(2～4)：1；进一步地，本发明所述脂环醇丙烯酸酯选自丙烯酸丁酯和丙辛酸异辛酯的重量比为3：1。
更进一步优选地，本发明所述脂环醇丙烯酸酯为甲基丙烯酸异冰片酯。
在一种优选的实施方式中，本发明所述双官能度活性稀释剂包括己二醇二丙烯酸酯和新戊二醇聚甲基环氧乙烷二丙烯酸酯，重量比为(2～3)：1；进一步地，本发明所述己二醇二丙烯酸酯和新戊二醇聚甲基环氧乙烷二丙烯酸酯的重量比为2：1。
新戊二醇聚甲基环氧乙烷二丙烯酸酯(CAS号：84170-74-1)为丙氧基化的新戊二醇二丙烯酸酯，具有好的稀释性和低粘度。
本发明所述预聚体具有较高的分子量和粘度，通过添加活性稀释剂对预聚体进行稀释，降低预聚体的粘度，促进预聚体和活性稀释剂的均匀分散，在固化过程中，由于本发明制备得到的预聚体具有较硬的核心，且壳层由于功能单体的高的分子间作用力和交联等作用，使得活性稀释剂容易在预聚体核壳结构的表面进行聚合，通过添加具有大侧基的甲基丙烯酸异冰片酯和含有长侧基的丙烯酸酯共同作用，作为单官能度活性稀释剂，由于异冰片酯取代基大的位组作用，可增加内聚强度，可减少长侧基的丙烯酸酯，如丙烯酸丁酯和丙烯酸异辛酯之间的缠结，从而增强韧性，且当双官能度活性稀释剂发生交联时，由于大侧基的甲基丙烯酸异冰片酯和长侧基的作用，也可防止生成局部较密的交联网络，从而导致缺陷，降低内聚强度。另外，申请人发现，当添加了适量的双官能度活性稀释剂，尤其是含有不同链长的双官能度活性稀释剂，如己二醇二丙烯酸酯、新戊二醇聚甲基环氧乙烷二丙烯酸酯，可形成疏密相间的交联体系，当受到多次弯曲时，剪切力会受到己二醇二丙烯酸酯形成的较密交联网络和新戊二醇聚甲基环氧乙烷二丙烯酸酯的较疏交联网络的共同传递，从而降低光学透明胶分子链的破环，增加多次弯折时的剥离强度和柔韧性。
光引发剂
光引发剂是一类能在紫外光区(250～420nm)或可见光区(400～800nm)吸收一定波长的能量，产生自由基、阳离子等，从而引发单体聚合交联固化的化合物。本发明不对光引发剂做具体限定，可列举的有，2959光引发剂、184光引发剂、1173光引发剂、907光引发剂、TPO光引发剂、TPO-L光引发剂、IHT-PI 910光引发剂、659光引发剂、MBF光引发剂、IHT-PI 4265光引发剂、IHT-PI 1000光引发剂、IHT-PI 500光引发剂。
在一种实施方式中，本发明所述光引发剂包括2959光引发剂和1173光引发剂，重量比为(1～2)：(0.3～0.8)；进一步地，本发明所述2959光引发剂和1173光引发剂，重量比为1.2：0.5。
本发明通过控制预聚体的制备、活性稀释剂的种类，从而调控制备得到的液态光学透明胶的玻璃化转变温度在-50～-20℃之间，其中，本发明所述玻璃化转变温度为根据DSC进行测试，从而满足固体光学透明胶的制备，以及在电子或电气领域的应用。
本发明第二个方面提供如上所述的液态光学透明胶的制备方法，包括以下步骤：
将所述液态光学透明胶的制备原料混合，得到所述液态光学透明胶。
本发明第三个方面提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
本发明通过将液态光学透明胶(LOCA)在离型膜上进行涂布，根据玻璃化温度选择合适的烘箱温度进行烘干，再通过UV固化装置进行固化，得到固态光学透明胶(OCA)厚度可以是25～100μm，可列举的有25μm、50μm、75μm、100μm，该固态光学透明胶可以用压合机将其与PC、CPI(透明聚酰亚胺)、PI、PMMA、PET等材质的面板进行压合，具有好的粘结性、韧性、最大应变和回弹性，且具有合适的内聚强度，对于上万次弯折不会出现剥离、气泡、翻折等现象。
本发明第四个方面提供如上所述的液态光学透明胶的应用，应用在电子或电气领域。
本发明所述的液态光学透明胶通过各制备原料的共同作用，以控制好剥离强度，韧性、粘性以及其内聚强度，可应用在电子或电气领域，尤其适合用于触摸 屏各面板之间的压合。
实施例
下面通过实施例对本发明进行具体描述。有必要在此指出的是，以下实施例只用于对本发明作进一步说明，不能理解为对本发明保护范围的限制，该领域的专业技术人员根据上述本发明的内容做出的一些非本质的改进和调整，仍属于本发明的保护范围。
实施例1
本发明的实施例1提供一种液态光学透明胶，所述液态光学透明胶的制备原料按重量份计，包括55份预聚体、12份活性稀释剂和1.5份光引发剂。
所述预聚体的制备原料包括丙烯酸酯单体和功能单体，所述丙烯酸酯单体包括硬单体和软单体，重量比为2：3，所述硬单体为甲基丙烯酸甲酯和丙烯酸，重量比为1：0.2，所述软单体为丙烯酸-2-乙基己酯和丙烯酸丁酯，重量比为1：2，所述功能单体占所述丙烯酸酯单体的5wt％，所述功能单体包括N-甲基(甲基)丙烯酰胺、己内酯丙烯酸酯、十二烷基硫醇和二缩三丙二醇二丙烯酸酯，重量比为2：2：0.02：0.025。所述预聚体的制备方法包括以下步骤：将15wt％硬单体、5wt％软单体、二缩三丙二醇二丙烯酸酯、十二烷基硫醇和过氧化二苯甲酰加入乙酸乙酯中混合，在75℃反应0.5h，滴加剩余硬单体和软单体后，加入N-甲基(甲基)丙烯酰胺和己内酯丙烯酸酯，回流，每隔0.5h测定碘值，当碘值趋于稳定时加入对苯二酚，得到预聚体；所述过氧化二苯甲酰占所述丙烯酸单体的0.5wt％。
所述活性稀释剂包括单官能度活性稀释剂和双官能度活性稀释剂，重量比为10：1，所述单官能度活性稀释剂包括甲基丙烯酸异冰片酯和烷基醇丙烯酸酯，重量比为1：2，所述脂环醇丙烯酸酯选自丙烯酸丁酯和丙辛酸异辛酯，重量比为4：1，所述双官能度活性稀释剂包括己二醇二丙烯酸酯和新戊二醇聚甲基环氧乙烷二丙烯酸酯，重量比为3：1。
所述光引发剂包括2959光引发剂和1173光引发剂，重量比为1：0.8。
本例还提供如上所述的液态光学透明胶的制备方法，包括以下步骤：
将所述液态光学透明胶的制备原料混合，得到所述液态光学透明胶。
本例还提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
实施例2
本发明的实施例2提供一种液态光学透明胶，所述液态光学透明胶的制备原料按重量份计，包括45份预聚体、6份活性稀释剂和1份光引发剂。
所述预聚体的制备原料包括丙烯酸酯单体和功能单体，所述丙烯酸酯单体包括硬单体和软单体，重量比为3：2，所述硬单体为甲基丙烯酸甲酯和丙烯酸，重量比为1：0.1，所述软单体为丙烯酸-2-乙基己酯和丙烯酸丁酯，重量比为2：1，所述功能单体占所述丙烯酸酯单体的3wt％，所述功能单体包括N-甲基(甲基)丙烯酰胺、己内酯丙烯酸酯、十二烷基硫醇和二缩三丙二醇二丙烯酸酯，重量比为1：1：0.01：0.01。所述预聚体的制备方法包括以下步骤：将15wt％硬单体、5wt％软单体、二缩三丙二醇二丙烯酸酯、十二烷基硫醇和过氧化二苯甲酰加入乙酸乙酯中混合，在75℃反应0.5h，滴加剩余硬单体和软单体后，N-甲基(甲基)丙烯酰胺和己内酯丙烯酸酯，回流，每隔0.5h测定碘值，当碘值趋于稳定时加入对苯二酚，得到预聚体；所述过氧化二苯甲酰占所述丙烯酸单体的0.5wt％。
所述活性稀释剂包括单官能度活性稀释剂和双官能度活性稀释剂，重量比为6：1，所述单官能度活性稀释剂包括甲基丙烯酸异冰片酯和烷基醇丙烯酸酯，重量比为2：1，所述脂环醇丙烯酸酯选自丙烯酸丁酯和丙辛酸异辛酯，重量比为4：1，所述双官能度活性稀释剂包括己二醇二丙烯酸酯和新戊二醇聚甲基环氧乙烷二丙烯酸酯，重量比为3：1。
所述光引发剂包括2959光引发剂和1173光引发剂，重量比为2：0.3。
本例还提供如上所述的液态光学透明胶的制备方法，包括以下步骤：
将所述液态光学透明胶的制备原料混合，得到所述液态光学透明胶。
本例还提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
实施例3
本发明的实施例3提供一种液态光学透明胶，所述液态光学透明胶的制备原料按重量份计，包括50份预聚体、9份活性稀释剂和1.2份光引发剂。
所述预聚体的制备原料包括丙烯酸酯单体和功能单体，所述丙烯酸酯单体包括硬单体和软单体，所述硬单体和软单体的重量比为1：1，所述硬单体为甲基丙烯酸甲酯和丙烯酸，重量比为1：0.13，所述软单体为丙烯酸-2-乙基己酯和丙 烯酸丁酯，重量比为1：1，所述功能单体占所述丙烯酸酯单体的4.05wt％，所述功能单体包括N-甲基(甲基)丙烯酰胺、己内酯丙烯酸酯、十二烷基硫醇和二缩三丙二醇二丙烯酸酯，重量比为2：2：0.02：0.025。所述预聚体的制备方法包括以下步骤：将15wt％硬单体、5wt％软单体、二缩三丙二醇二丙烯酸酯、十二烷基硫醇和过氧化二苯甲酰加入乙酸乙酯中混合，在75℃反应0.5h，滴加剩余硬单体和软单体后，加入N-甲基(甲基)丙烯酰胺和己内酯丙烯酸酯，回流，每隔0.5h测定碘值，当碘值趋于稳定时加入对苯二酚，得到预聚体；所述过氧化二苯甲酰占所述丙烯酸单体的0.5wt％。
所述活性稀释剂包括单官能度活性稀释剂和双官能度活性稀释剂，重量比为8：1，所述单官能度活性稀释剂包括甲基丙烯酸异冰片酯和烷基醇丙烯酸酯，重量比为1：1，所述脂环醇丙烯酸酯选自丙烯酸丁酯和丙辛酸异辛酯，重量比为3：1，所述双官能度活性稀释剂包括己二醇二丙烯酸酯和新戊二醇聚甲基环氧乙烷二丙烯酸酯，重量比为2：1。
所述光引发剂包括2959光引发剂和1173光引发剂，重量比为1.2：0.5。
本例还提供如上所述的液态光学透明胶的制备方法，包括以下步骤：
将所述液态光学透明胶的制备原料混合，得到所述液态光学透明胶。
本例还提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
实施例4
本发明的实施例4提供一种液态光学透明胶，所述液态光学透明胶的制备原料按重量份计，包括50份预聚体、9份活性稀释剂和1.2份光引发剂。
所述预聚体的制备原料包括丙烯酸酯单体和功能单体，所述丙烯酸酯单体包括硬单体和软单体，所述硬单体和软单体的重量比为1：1，所述硬单体为甲基丙烯酸甲酯和丙烯酸，重量比为1：0.13，所述软单体为丙烯酸-2-乙基己酯和丙烯酸丁酯，重量比为1：1，所述功能单体占所述丙烯酸酯单体的0.05wt％，所述功能单体包括十二烷基硫醇和二缩三丙二醇二丙烯酸酯，重量比为0.8：1。所述预聚体的制备方法包括以下步骤：将15wt％硬单体、5wt％软单体二缩三丙二醇二丙烯酸酯、十二烷基硫醇和过氧化二苯甲酰加入乙酸乙酯中混合，在75℃反应0.5h，滴加剩余硬单体和软单体后，回流0.5h，得到预聚体；所述过氧化二苯 甲酰占所述丙烯酸单体的0.5wt％。
所述活性稀释剂包括单官能度活性稀释剂和双官能度活性稀释剂，重量比为8：1，所述单官能度活性稀释剂包括甲基丙烯酸异冰片酯和烷基醇丙烯酸酯，重量比为1：1，所述脂环醇丙烯酸酯选自丙烯酸丁酯和丙辛酸异辛酯，重量比为3：1，所述双官能度活性稀释剂包括己二醇二丙烯酸酯和新戊二醇聚甲基环氧乙烷二丙烯酸酯，重量比为2：1。
所述光引发剂包括2959光引发剂和1173光引发剂，重量比为1.2：0.5。
本例还提供如上所述的液态光学透明胶的制备方法，包括以下步骤：
将所述液态光学透明胶的制备原料混合，得到所述液态光学透明胶。
本例还提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
对比例1
本发明的对比例1提供一种液态光学透明胶，其具体实施方式同实施例3，不同之处在于，所述丙烯酸替换为3-羟基-1-金刚烷基甲基丙烯酸酯。
本例还提供如上所述的液态光学透明胶的制备方法，其具体实施方式同实施例3。
本例还提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
对比例2
本发明的对比例2提供一种液态光学透明胶，其具体实施方式同实施例3，不同之处在于，所述丙烯酸丁酯替换为丙烯酸十二烷酯。
本例还提供如上所述的液态光学透明胶的制备方法，其具体实施方式同实施例3。
本例还提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
对比例3
本发明的对比例3提供一种液态光学透明胶，其具体实施方式同实施例3，不同之处在于，所述N-甲基(甲基)丙烯酰胺替换成N-己基(甲基)丙烯酰胺。
本例还提供如上所述的液态光学透明胶的制备方法，其具体实施方式同实施 例3。
对比例4
本发明的对比例4提供一种液态光学透明胶，其具体实施方式同实施例3，不同之处在于，所述N-甲基(甲基)丙烯酰胺替换成N,N-二甲基(甲基)丙烯酰胺。
本例还提供如上所述的液态光学透明胶的制备方法，其具体实施方式同实施例3。
本例还提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
对比例5
本发明的对比例5提供一种液态光学透明胶，其具体实施方式同实施例3，不同之处在于，所述功能单体不包括N-甲基(甲基)丙烯酰胺。
本例还提供如上所述的液态光学透明胶的制备方法，其具体实施方式同实施例3。
本例还提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
对比例6
本发明的对比例6提供一种液态光学透明胶，其具体实施方式同实施例3，不同之处在于，所述功能单体不包括己内酯丙烯酸酯。
本例还提供如上所述的液态光学透明胶的制备方法，其具体实施方式同实施例3。
本例还提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
对比例7
本发明的对比例7提供一种液态光学透明胶，其具体实施方式同实施例3，不同之处在于，所述己内酯丙烯酸酯替换成丙烯酸-2-羟乙基酯。
本例还提供如上所述的液态光学透明胶的制备方法，其具体实施方式同实施例3。
本例还提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
对比例8
本发明的对比例8提供一种液态光学透明胶，其具体实施方式同实施例3，不同之处在于，所述预聚体的制备方法包括以下步骤：将硬单体、软单体和过氧化二苯甲酰混合，在75℃反应1h得到预聚体。
本例还提供如上所述的液态光学透明胶的制备方法，其具体实施方式同实施例3。
本例还提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
对比例9
本发明的对比例9提供一种液态光学透明胶，其具体实施方式同实施例3，不同之处在于，所述预聚体的制备方法包括以下步骤：将10wt％硬单体、10wt％软单体和过氧化二苯甲酰混合，在75℃反应0.5h，滴加剩余硬单体和软单体后，加入功能单体，回流0.5h，得到预聚体。
本例还提供如上所述的液态光学透明胶的制备方法，其具体实施方式同实施例3。
本例还提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
对比例10
本发明的对比例10提供一种液态光学透明胶，其具体实施方式同实施例3，不同之处在于，所述双官能度活性稀释剂不包括新戊二醇聚甲基环氧乙烷二丙烯酸酯。
本例还提供如上所述的液态光学透明胶的制备方法，其具体实施方式同实施例3。
本例还提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
对比例11
本发明的对比例11提供一种液态光学透明胶，其具体实施方式同实施例3，不同之处在于，所述双官能度活性稀释剂不包括己二醇二丙烯酸酯。
本例还提供如上所述的液态光学透明胶的制备方法，其具体实施方式同实施 例3。
本例还提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
对比例12
本发明的对比例12提供一种液态光学透明胶，其具体实施方式同实施例3，不同之处在于，所述新戊二醇聚甲基环氧乙烷二丙烯酸酯替换成二缩三丙二醇二丙烯酸酯。
本例还提供如上所述的液态光学透明胶的制备方法，其具体实施方式同实施例3。
本例还提供一种固态光学透明胶，由如上所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
对比例13
本发明的对比例13提供固态光学透明胶，所述固态光学透明胶的牌号为FINESET TE227，所述固态光学透明胶的厚度为50μm。
性能评价
1、动态弯折测试：将实施例1～4和对比例1～12提供的固态光学透明胶通过Yuasa弯折测试机进行动态弯折测试，将50μm固态光学透明胶撕掉离型膜面，覆上25μmPI/50μmPI膜压合，观察R＝2mm，180°弯折15万次、20万次、25万次是否有剥离、气泡、翻折现象，其中O为无剥离、气泡、翻折现象，X为有剥离、气泡、翻折现象，结果见表1。
2、静态弯折测试：将实施例1～3提供的固态光学透明胶通过Yuasa弯折测试机观察静态弯折(外折R4/内弯R2，测试环境60℃，90％湿度，静置240hrs)后是否有裂纹、白化现象，发现实施例1～3提供的固态光学透明胶无裂纹、白化现象。
3、剥离强度：将实施例1～4和对比例1～13提供的固态光学透明胶根据GB T 2792-1998通过日本ORIENTEC拉力试验机测试剥离强度，将50μm固态光学透明胶撕掉离型膜面，覆上25μmPET/25μmCPI膜压合，测试25℃，R＝2mm，180°弯折15万次、20万次弯折前后的的180°剥离强度，结果见表1。
4、透光色度：将实施例1～4和对比例4～6提供的固态光学透明胶通过分 光光度计V-670测试透光色度，并根据色度指标L*、a*、b*进行评价，其中O为色度指标L*≥97％、a*＝0.0±0.5、b*＝0.2±0.5，X为色度指标不在L*≥97％、a*＝0.0±0.5、b*＝0.2±0.5的范围内，结果见表1。
5、性能测试：将实施例1～3提供的固态光学透明胶进行光学性能、机械性能、腐蚀性性能测试，发现满足触摸屏用固态光学透明胶的规格要求，性能测试方法及标准见表2。
表1性能表征测试
Figure PCTCN2020110713-appb-000001
表2性能表征测试
Figure PCTCN2020110713-appb-000002
Figure PCTCN2020110713-appb-000003
Figure PCTCN2020110713-appb-000004
由表1和表2测试结果可知，本发明提供的液态光学透明胶具有高的韧性、剥离强度和色度，其动态弯折20万次以上无无剥离、气泡、翻折，且在动态弯折20万次后其剥离强度在15N/25mm，而对比例13提供的光学透明胶虽然具有好的韧性，但是其粘结性较弱，尤其是处于运动状态或者多次弯折时粘结性较差；另外，本发明提供的液态光学透明胶可用于触摸屏，尤其是显示面板、显示屏组、显示柔性屏的粘结，且具有高的应变和回弹性，并具有适合的内聚强度。
前述的实例仅是说明性的，用于解释本发明所述方法的一些特征。所附的权利要求旨在要求可以设想的尽可能广的范围，且本文所呈现的实施例仅是根据所有可能的实施例的组合的选择的实施方式的说明。因此，申请人的用意是所附的权利要求不被说明本发明的特征的示例的选择限制。在权利要求中所用的一些数值范围也包括了在其之内的子范围，这些范围中的变化也应在可能的情况下解释为被所附的权利要求覆盖。

Claims (10)

  1. 一种液态光学透明胶，其特征在于，所述液态光学透明胶的制备原料按重量份计，包括45～55份预聚体、6～12份活性稀释剂和1～1.5份光引发剂。
  2. 根据权利要求1所述的液态光学透明胶，其特征在于，所述预聚体的制备原料包括丙烯酸酯单体和功能单体，所述丙烯酸酯单体包括硬单体和软单体，重量比为(2～3)：(2～3)。
  3. 根据权利要求2所述的液态光学透明胶，其特征在于，所述功能单体占所述丙烯酸酯单体的0.01～5wt％，所述功能单体包括链转移剂和交联单体，所述链转移剂和交联单体的重量比为(0.5～1)：1。
  4. 根据权利要求2所述的液态光学透明胶，其特征在于，所述预聚体的制备方法包括以下步骤：
    将15～20wt％硬单体、5～10wt％软单体、交联单体、链转移剂和引发剂加入溶剂中，在70～80℃反应0.4～0.6h，滴加剩余硬单体和软单体反应，得到预聚体。
  5. 根据权利要求4所述的液态光学透明胶，其特征在于，所述功能单体还包括丙烯酰胺和羟基丙烯酸酯，所述丙烯酰胺、羟基丙烯酸酯和链转移剂的重量比为(1～2)：(1～2)：(0.01～0.2)。
  6. 根据权利要求1～5任意一项所述的液态光学透明胶，其特征在于，所述活性稀释剂包括单官能度活性稀释剂和双官能度活性稀释剂，重量比为(6～10)：1。
  7. 根据权利要求6所述的液态光学透明胶，其特征在于，所述双官能度活性稀释剂包括己二醇二丙烯酸酯和新戊二醇聚甲基环氧乙烷二丙烯酸酯，重量比为(2～3)：1。
  8. 一种根据权利要求1～7任意一项所述的液态光学透明胶的制备方法，其特征在于，包括以下步骤：
    将所述液态光学透明胶的制备原料混合，得到所述液态光学透明胶。
  9. 一种固态光学透明胶，其特征在于，由权利要求1～7任意一项所述的液态光学透明胶涂布在离型膜上、烘干、UV固化制备得到。
  10. 一种根据权利要求1～7任意一项所述的液态光学透明胶的应用，其特征在于，应用在电子或电气领域。
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CN112175526A (zh) * 2020-10-28 2021-01-05 南京汇鑫光电材料有限公司 一种低介电oca光学胶
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