CN117925154A - Folding-resistant OCA optical pressure-sensitive adhesive and preparation method thereof - Google Patents
Folding-resistant OCA optical pressure-sensitive adhesive and preparation method thereof Download PDFInfo
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- CN117925154A CN117925154A CN202311690043.2A CN202311690043A CN117925154A CN 117925154 A CN117925154 A CN 117925154A CN 202311690043 A CN202311690043 A CN 202311690043A CN 117925154 A CN117925154 A CN 117925154A
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- acrylate
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- sensitive adhesive
- oca optical
- methacrylate
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- 230000003287 optical effect Effects 0.000 title claims abstract description 56
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 229920001400 block copolymer Polymers 0.000 claims abstract description 16
- 238000013467 fragmentation Methods 0.000 claims abstract description 8
- 238000006062 fragmentation reaction Methods 0.000 claims abstract description 8
- 230000002441 reversible effect Effects 0.000 claims abstract description 8
- 238000012546 transfer Methods 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 25
- 230000001070 adhesive effect Effects 0.000 claims description 24
- 239000000853 adhesive Substances 0.000 claims description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
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- 238000002834 transmittance Methods 0.000 claims description 10
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- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
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- 229920006030 multiblock copolymer Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
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- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052786 argon Inorganic materials 0.000 claims description 4
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- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- RXBOCDZLKBPILN-UHFFFAOYSA-N 2-propylheptyl prop-2-enoate Chemical compound CCCCCC(CCC)COC(=O)C=C RXBOCDZLKBPILN-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- DZGUJOWBVDZNNF-UHFFFAOYSA-N azanium;2-methylprop-2-enoate Chemical compound [NH4+].CC(=C)C([O-])=O DZGUJOWBVDZNNF-UHFFFAOYSA-N 0.000 claims description 2
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000005022 dithioester group Chemical group 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 229940065472 octyl acrylate Drugs 0.000 claims description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a folding-resistant OCA optical pressure-sensitive adhesive and a preparation method thereof. The block copolymer adopts reversible addition fragmentation chain transfer emulsion polymerization, and has the characteristics of controllable molecular structure design and high molecular weight. After being blended with auxiliary agents such as tackifying resin, the folding resistance is obviously improved. The OCA optical pressure-sensitive adhesive prepared by the invention has the storage modulus of not more than 100kPa in the temperature range of minus 30-90 ℃, the peeling strength of not less than 10N/25mm, the strain recovery rate of not less than 95% after the applied stress is removed for 1h after the tensile strain is kept for 1h in the range of 100-500%, and the folding-resistant times of not less than 30 ten thousand times, and is suitable for curved screens, folding-resistant screens, crimpable screen mobile phones and wearable equipment.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a folding-resistant OCA optical pressure-sensitive adhesive and a preparation method thereof.
Background
The optical pressure-sensitive adhesive (Optically CLEAR ADHESIVE, OCA) is widely applied to the bonding of terminal electronic functional devices, and generally has optical transmittance of more than 90% and high bonding strength. The OCA can fill the air gap to reduce the refractive index difference, thereby contributing to the improvement of the sharpness of the image display. In recent years, with the advent of curved screen, foldable screen and curled screen mobile phones, the realization of the folding resistance of OCA has become the latest research hot spot. The traditional OCA has the characteristics of higher modulus, strong adhesive property and the like, and cracks can appear on a screen when the traditional OCA is applied to a foldable mobile phone. Compared with the traditional optical adhesive, the folding-resistant OCA optical adhesive not only needs to meet the requirement of high adhesive property, but also needs to have low modulus. In addition, in order to reduce the creases, the optical adhesive is required to have high rebound resilience.
Currently commercially available fold-resistant pressure-sensitive adhesives typically employ low density chemically crosslinked networks. However, the number of functional groups in the chemically crosslinked network is low, and the crosslinked network is incomplete, resulting in poor rebound resilience of the polymer. In addition, pressure-sensitive adhesives with low chemical crosslinking networks generally have low cohesive forces, are prone to cohesive failure during peel testing, and have low peel strength. The existence of the contradictory relationship between low modulus and high resilience and high peel strength is a difficulty and challenge in designing fold resistant optical adhesives. The block copolymer crosslinking point has higher functionality, is a new method for preparing the optical pressure-sensitive adhesive in recent years, and compared with the traditional UV light-cured pressure-sensitive adhesive, the product has a complete crosslinking network, and can prepare the optical adhesive with ultra-low modulus and ultra-high rebound resilience.
However, the block copolymer itself has limited peel strength, which leads to the problem of easy degluing during application, resulting in reduced folding resistance. In order to further improve the folding resistance of the optical adhesive, a technology capable of preparing the optical adhesive which can be folded for hundreds of thousands times is needed, and further, the folding resistance of the optical adhesive is improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method for enhancing the folding resistance of an OCA optical pressure-sensitive adhesive. The method is to blend the segmented copolymer with auxiliary agents such as tackifying resin and the like, and prepare the OCA optical pressure-sensitive adhesive with high stretchability, high transparency, low haze and excellent folding resistance through solution film formation. The addition of the tackifying resin can greatly improve the peeling strength and the folding resistance of the material on the basis of not reducing the rebound resilience and not improving the modulus.
The invention is realized by the following technical scheme:
the folding-resistant OCA optical pressure-sensitive adhesive is prepared by dissolving 50-100 parts of multiblock copolymer, 0-50 parts of tackifying resin and 0-20 parts of other additives in a dispersion medium, uniformly coating a glue solution on a heavy release layer in an argon environment, drying, and covering a light release layer on the upper layer.
Specifically, the structural general formula of the multiblock copolymer is M 1-b-M2-b-M3……-b-Mj, wherein the value range of j is 3-11; wherein M 1、M2、M3……Mj is a comonomer in the block copolymer, and the number average molecular weight of the block copolymer of the main matrix is 8-80 ten thousand g/mol; m 1、M2、M3……Mj is selected from soft monomer, hard monomer or functional monomer respectively; the mass contents of the soft monomer, the hard monomer and the functional monomer in the block copolymer are respectively 70-98%, 2-30% and 0-5%;
Specifically, the hard monomers include, but are not limited to, styrene, methyl acrylate, isobornyl acrylate, methyl methacrylate, acrylamide, acrylonitrile, and vinyl acetate, with a glass transition temperature in the range of 60-150 ℃; the soft monomers include, but are not limited to, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, n-butyl methacrylate, octyl acrylate, 2-propylheptyl acrylate, isobutyl methacrylate, t-butyl methacrylate, isooctyl methacrylate, butadiene, isoprene, ethylene-butene, and methacrylic acid, with a glass transition temperature in the range of-90 to-30 ℃; the functional monomers include, but are not limited to, methacrylic acid, acrylic acid, itaconic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, ethylenedimethylamine methacrylate, amine methacrylate, N-methylolacrylamide, glycidyl methacrylate, and maleic anhydride.
Further, the types of the tackifying resin include, but are not limited to DMER-95, GA-90, GA-100, GB-120, TP2019, T801 and T801/L, and the optical adhesive prepared by the tackifying resin has light transmittance of more than 90% and haze of less than 1%.
Further, the other auxiliary agents include but are not limited to antioxidants, printing ink and ultraviolet screening agents, and the prepared optical adhesive has light transmittance of more than 90% and haze of less than 1%.
Further, the dispersion medium includes, but is not limited to, butanone, diethyl ether, methyl tertiary butyl ether, tetrahydrofuran, methyl ethyl ketone, ethyl acetate, and methyl propionate.
The invention also provides a preparation method of the folding-resistant OCA optical pressure-sensitive adhesive, which comprises the following steps:
(1) Dissolving an amphiphilic macromolecule reversible addition fragmentation chain transfer reagent in water, then adding styrene or styrene and methacrylic acid, stirring until the mixture is uniform, adding a first initiator at 70-90 ℃, and reacting for 1-3 hours to obtain a homopolymer, wherein the homopolymer is stably dispersed in the water in a particle form to form latex;
The chemical structural formula of the amphiphilic macromolecule reversible addition fragmentation chain transfer reagent is as follows: r- (M n1-b-Nn2) -X; wherein R is isopropyl, acetoxy, 2-cyanoacetoxy or 2-amino acetoxy; in M n1, M is methacrylic acid monomer or acrylic acid monomer unit, n1 is average polymerization degree of M, and n1 ranges from 10to 30; in N n2, N is a styrene monomer, an N-butyl acrylate monomer, methyl acrylate, isooctyl acrylate or methyl methacrylate monomer unit, N2 is the average polymerization degree of N, and the range of N2 is 1-8; the X group is an alkyl dithioester group or an alkyl trithioester group;
(2) Adding 10wt% concentration sodium hydroxide aqua, adding isooctyl acrylate or isooctyl acrylate and methacrylic acid, adding water, adding second initiator at 40-60 deg.c for reaction in anaerobic environment for 3-10 hr, adding hard monomer and reaction in anaerobic environment for 5-10 hr to obtain main matrix polymer latex;
(3) After the reaction, the polymer latex, 30wt% hydrogen peroxide and 7.5wt% hydrochloric acid are mixed according to the volume ratio of 3:2:3, placing the mixture in a beaker, stirring the mixture for 15min until the mixture is uniform, heating the mixture to 50 ℃, and reacting the mixture for 1.5 to 3 hours; washing the precipitate with distilled water to neutrality, air drying, vacuum drying in a vacuum oven at 120deg.C for 5-20 hr to obtain multiblock copolymer;
(4) After the reaction, the polymer latex, 30wt% hydrogen peroxide and 7.5wt% hydrochloric acid are mixed according to the volume ratio of 2:1:2, placing the mixture in a beaker, stirring the mixture for 15min until the mixture is uniform, heating the mixture to 40-60 ℃, and reacting the mixture for 1.5-3h; washing the precipitate with distilled water for several times to neutrality, air drying, vacuum drying in a vacuum oven at 120deg.C for 5-20 hr to obtain reinforced matrix;
(5) And dissolving the multiblock copolymer, tackifying resin and other assistants in a dispersion medium, coating the mixture into a film in an argon environment, and drying the film to finally obtain the OCA optical adhesive.
The beneficial effects of the invention are as follows:
The block copolymer is prepared by adopting a reversible addition fragmentation chain transfer emulsion polymerization controllable design to serve as a folding-resistant OCA optical pressure-sensitive adhesive matrix, and the folding resistance of the optical adhesive is improved by adding tackifying resin. The tackifying resin has good compatibility with the block copolymer, and the addition of the block copolymer can greatly improve the peeling strength of the optical adhesive, and can not cause the reduction of light transmittance, the increase of modulus and the reduction of rebound resilience. The method for improving the formula is low in cost and can be industrialized, the folding resistance of the optical adhesive can be effectively improved through compounding the synthesized segmented copolymer, and the optical adhesive is assembled in curved-surface screens, folding-resistant screens, crimpable-screen mobile phones and wearable equipment. The addition of the tackifying resin does not affect the characteristics of high transparency, high stretchability, low haze, ageing resistance and the like of the folding-resistant OCA optical pressure-sensitive adhesive.
Drawings
FIG. 1 is a GPC chart of a block copolymer obtained in the present invention;
FIG. 2 is a mechanical stretch graph of an OCA optical pressure sensitive adhesive made in accordance with the present invention;
FIG. 3 is a graph of stress relaxation recovery for an OCA optical pressure sensitive adhesive made in accordance with the present invention; wherein, (a) is a stress recovery graph; (b) graph is stress relaxation graph; (c) stress relaxation rate and strain recovery rate;
FIG. 4 is a graph of the shear dynamic mechanical properties of the OCA optical pressure sensitive adhesive obtained by the invention; wherein (a) is a plot of modulus (storage modulus and dissipation modulus) versus angular frequency; (b) graph is the variation graph of loss factor with angular frequency;
FIG. 5 is a graph of peel strength results for OCA optical pressure sensitive adhesives made in accordance with the present invention.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention are further described, but the present invention is not limited to these examples.
Example 1: preparation and Properties of Poly (styrene-b-isooctyl acrylate-b-styrene) Block copolymer
The embodiment adopts a RAFT reversible addition fragmentation chain transfer emulsion polymerization method to prepare materials, and comprises the following specific steps:
The first step: stirring 1 part by mass of an amphiphilic macromolecule RAFT reagent (amphiphilic macromolecule reversible addition fragmentation chain transfer reagent) and 13 parts by mass of water until the amphiphilic macromolecule RAFT reagent and the amphiphilic macromolecule RAFT reagent are completely dissolved, then adding 6 parts by mass of styrene or adding 6 parts by mass of styrene and one part by mass of methacrylic acid, wherein the addition of the methacrylic acid is used for improving the adhesiveness between monomers, and then stirring and mixing, wherein the amphiphilic macromolecule RAFT reagent has a chemical structural formula as follows:
And a second step of: the raw materials are added into a four-neck flask, nitrogen is introduced at room temperature to remove oxygen for 0.5h, the temperature is raised to 70 ℃ in a water bath, and an initiator potassium persulfate aqueous solution (0.02 mass part of potassium persulfate is dissolved in 12 mass parts of water) is added for reaction for 1h. Then, an aqueous sodium hydroxide solution (1 part by mass of sodium hydroxide was dissolved in 10 parts by mass of water) was slowly added, followed by addition of 90 parts by mass of isooctyl acrylate and 50 parts by mass of water, and then addition of 0.02 part by mass of azobisiso Ding Mi. Sup. Ne hydrochloride, followed by reaction for 2 hours. Finally, adding 7 parts by mass of styrene, and reacting for 1.5 hours to obtain polymer latex;
And a third step of: the polymer latex, 30wt% hydrogen peroxide and 7.5wt% hydrochloric acid are mixed according to the volume ratio of 2:1:2 is placed in a beaker, stirred for 15min until uniform, heated to 50 ℃ and reacted for 1.5h in an air environment.
Fourth step: washing the sedimentation product with distilled water for a plurality of times to neutrality after the reaction is finished, airing, and then placing the sedimentation product in a vacuum oven at 120 ℃ for vacuum drying for 12 hours to finally obtain white polymer particles;
Fifth step: dissolving the polymer in butanone, pouring the polymer into a polytetrafluoroethylene surface dish with the diameter of 12cm to form a film, volatilizing most of the solvent at room temperature, and then placing the film in a vacuum oven with the temperature of 130 ℃ to continuously dry and anneal to prepare the polymer film with the thickness of about 0.8-1 mm.
Sixth step: the polymer was dissolved in butanone and an OCA optical pressure sensitive adhesive film having a thickness of about 25 μm was prepared by a bar coater for peel strength testing.
The molecular weight characterization of the polymer was performed on a gel permeation chromatography Waters1525-2414-717GPC instrument, with tetrahydrofuran as eluent, calibrated with narrow distribution polystyrene standards.
The mechanical properties of the polymer are tested by a universal material testing machine (Zwick/Roll Z020), the polymer film in the fourth step is cut into dumbbell-shaped sample bars by a standard sample cutter for standby, the testing method adopts GB 16421-1996, the stretching rate is 30mm/min, and the test of each sample is repeated at least three times.
The polymer was tested for stress relaxation recovery properties with DMA (TAQ 800), the OCA optical pressure-sensitive adhesive film of the fourth step was cut into strips having a width of 5mm and a length of 25mm, and the OCA optical pressure-sensitive adhesive was respectively tested for stretching for 1h at a strain of 100%,200%,300%,400%,500%, and then maintained for 1h at a stress of 0MPa, and its recovery curve was recorded.
The dynamic mechanical properties of the polymer were characterized by a rotational rheometer (HAAKE MARS, 60), and the polymer film was cut into round bars with a diameter of 2cm, with a test frequency of 0.01Hz-1Hz, and a test temperature of 25 ℃. The loss factor tan delta of the material is recorded during the measurement.
The peel strength of the polymer was tested by an adhesive shear strength tester (KJ-1066A), the OCA optical pressure-sensitive adhesive film of the fifth step was cut into strips with a width of 25mm and a length of about 300mm, and the test was repeated at least three times for each sample using GB/T2792-2014.
The folding resistance of the polymer was measured by a temperature and humidity bending endurance tester (Beijing Wo Huahui, measurement and control technologies Co., ltd.). Two layers of PET with the thickness of 50 mu m are respectively stuck on two sides of the adhesive film, so that bubbles generated in the sticking process are reduced as much as possible. Then cutting the sample into a strip sample with the width of 5cm and the length of 20cm, then adhering and fixing the two longer sides on a testing machine by using an adhesive tape, setting the bending angle to be 180 degrees, setting the testing frequency to be 60 times/min, setting the bending radius to be 3mm according to the requirement, recording the testing temperature, and performing experiment, wherein the testing temperature is 20+/-5 ℃, and the testing humidity is 50+/-5%.
The optical properties of the polymer were measured by an ultraviolet spectrophotometer (Cary 5000, agilent, usa) and the sample was cut into circles of 2mm diameter. The adhesive film and the glass sheet are respectively used as a test sample and a reference sample, the wavelength scanning range is 300-800nm, the glass sheet is required to be used as a background for light transmittance scanning before testing, then the prepared adhesive film is torn off to be attached to the glass sheet after the release protective film is removed, and then the release protective film is torn off to be scanned again for light transmittance.
FIG. 1 is a GPC curve of a block copolymer obtained after completion of each reaction, wherein curve 1 in the figure is polystyrene (PSt); curve 2 is poly (styrene-b-isooctyl acrylate) (PSt-PEHA); curve 3 is poly (styrene-b-isooctyl acrylate-b-styrene) (PSt-PEHA-PSt); it can be seen that as the number of blocks increases, the molecular weight of the polymer shifts overall toward higher molecular weights, indicating that the product is a block copolymer with a molecular weight of 1.2W to 20.0W to 1.2W, respectively. The mechanical properties of the block copolymer are shown in FIG. 2, which shows that the polymer has a low modulus of 118.8KPa, a low stress of 1.02MPa, and a high elongation at break of approximately 904%. FIG. 3 is a stress relaxation recovery curve of an OCA optical pressure sensitive adhesive, and FIG. 3 (a) is a stress recovery curve; fig. 3 (b) is a stress relaxation graph; fig. 3 (c) is a graph of stress relaxation rate and strain recovery rate; wherein (a) in fig. 4 is a graph of modulus (storage modulus and dissipation modulus) versus angular frequency; fig. 4 (b) is a graph showing the variation of the loss factor with angular frequency; it can be seen that at 300% tensile strain, the strain recovery exceeded 95%. FIG. 4 shows the shear dynamic mechanical properties of an OCA optical pressure sensitive adhesive with a shear modulus of only 22.6KPa. As shown in FIG. 5, the OCA optical pressure-sensitive adhesive film had a peel strength of 8.1N/25mm at a film thickness of 25. Mu.m.
As shown in table 1, it is the folding endurance of the OCA optical pressure-sensitive adhesive, and the number of folding endurance exceeds 20 ten thousand times.
TABLE 1
| Tackifying resin content/% | Number of fold resistance |
| 0％ | More than 20 ten thousand times |
| 10％ | More than 20 ten thousand times |
| 20％ | More than 20 ten thousand times |
| 30％ | More than 20 ten thousand times |
As shown in table 2, it is the optical performance of OCA optical cement, its light transmittance is more than 99%, and haze is less than 1%.
TABLE 2
| Tackifying resin content/% | Transmittance/% | Haze/% |
| 0％ | ＞99 | ＜1 |
| 10％ | ＞99 | ＜1 |
| 20％ | ＞99 | ＜1 |
| 30％ | ＞99 | ＜1 |
EXAMPLE 2 preparation and Properties of a blend of 90 parts of Poly (styrene-b-isooctyl acrylate-b-styrene) block copolymer and 10 parts of tackifying resin TP2019
The poly (styrene-b-isooctyl acrylate-b-styrene) block copolymer used in this example was the same as in example 1, 90 parts of the poly (styrene-b-isooctyl acrylate-b-styrene) block copolymer and 10 parts of tackifying resin TP2019 were dissolved in butanone, the glue solution was uniformly coated on the heavy release layer in an argon atmosphere, and after drying, a light release layer was covered on the upper layer, finally the OCA optical glue was obtained.
The polymer test characterization of this example is the same as that of example 1, and is shown as 10% in the legend.
Example 3: preparation and Properties of a blend of 80 parts of Poly (styrene-b-isooctyl acrylate-b-styrene) block copolymer and 20 parts of tackifying resin;
the blend of this example was prepared similarly to example 2, except that 80 parts of poly (styrene-b-isooctyl acrylate-b-styrene) block copolymer was used with 20 parts of tackifying resin dissolved in butanone.
The polymer test characterization of this example is the same as that of example 1, and is shown as 20% in the legend.
Example 4: preparation and Properties of a blend of 70 parts of Poly (styrene-b-isooctyl acrylate-b-styrene) block copolymer and 30 parts of tackifying resin;
The blend of this example was prepared similarly to example 2, except that 70 parts of poly (styrene-b-isooctyl acrylate-b-styrene) block copolymer was used with 30 parts of tackifying resin dissolved in butanone.
The polymer test characterization of this example is the same as that of example 1, and is shown as 30% in the legend.
The above-described embodiments are intended to illustrate the present invention, not to limit it, and any modifications and variations made thereto are within the spirit of the invention and the scope of the appended claims.
Claims (7)
1. The folding-resistant OCA optical pressure-sensitive adhesive is characterized in that 50-100 parts of multiblock copolymer, 0-50 parts of tackifying resin and 0-20 parts of other auxiliary agents are dissolved in a dispersion medium, glue solution is uniformly coated on a heavy release layer in an argon environment, and a light release layer is covered on the upper layer after drying, so that the OCA optical adhesive is obtained.
2. The folding-resistant OCA optical pressure-sensitive adhesive according to claim 1, wherein the multiblock copolymer has a structural formula of M 1-b-M2-b-M3……-b-Mj, wherein j has a value in the range of 3 to 11; wherein M 1、M2、M3……Mj is a comonomer in the block copolymer, and the number average molecular weight of the block copolymer of the main matrix is 8-80 ten thousand g/mol; m 1、M2、M3……Mj is selected from soft monomer, hard monomer or functional monomer respectively; and the mass contents of the soft monomer, the hard monomer and the functional monomer in the block copolymer are respectively 70-98%, 2-30% and 0-5%.
3. The fold-resistant OCA optical pressure-sensitive adhesive of claim 2, wherein the hard monomers include, but are not limited to, styrene, methyl acrylate, isobornyl acrylate, methyl methacrylate, acrylamide, acrylonitrile, and vinyl acetate, and have a glass transition temperature in the range of 60-150 ℃; the soft monomers include, but are not limited to, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, n-butyl methacrylate, octyl acrylate, 2-propylheptyl acrylate, isobutyl methacrylate, t-butyl methacrylate, isooctyl methacrylate, butadiene, isoprene, ethylene-butene, and methacrylic acid, with a glass transition temperature in the range of-90 to-30 ℃; the functional monomers include, but are not limited to, methacrylic acid, acrylic acid, itaconic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, ethylenedimethylamine methacrylate, amine methacrylate, N-methylolacrylamide, glycidyl methacrylate, and maleic anhydride.
4. The fold-resistant OCA optical pressure-sensitive adhesive according to claim 1, wherein the types of tackifying resins include, but are not limited to DMER-95, GA-90, GA-100, GB-120, TP2019, T801/L, and the optical adhesive prepared therefrom has a light transmittance of greater than 90% and a haze of less than 1%.
5. The fold-resistant OCA optical pressure-sensitive adhesive of claim 1, wherein the optical adhesive prepared by other additives including but not limited to antioxidants, inks, ultraviolet screening agents has a light transmittance of greater than 90% and a haze of less than 1%.
6. The fold-resistant OCA optical pressure-sensitive adhesive of claim 1, wherein the dispersing medium comprises, but is not limited to, methyl ethyl ketone, diethyl ether, methyl t-butyl ether, tetrahydrofuran, methyl ethyl ketone, ethyl acetate, and methyl propionate.
7. A method for preparing a folding-resistant OCA optical pressure-sensitive adhesive, which is characterized by comprising the following steps:
(1) Dissolving an amphiphilic macromolecule reversible addition fragmentation chain transfer reagent in water, then adding styrene or styrene and methacrylic acid, stirring until the mixture is uniform, adding a first initiator at 70-90 ℃, and reacting for 1-3 hours to obtain a homopolymer, wherein the homopolymer is stably dispersed in the water in a particle form to form latex;
The chemical structural formula of the amphiphilic macromolecule reversible addition fragmentation chain transfer reagent is as follows: r- (M n1-b-Nn2) -X; wherein R is isopropyl, acetoxy, 2-cyanoacetoxy or 2-amino acetoxy; in M n1, M is methacrylic acid monomer or acrylic acid monomer unit, n1 is average polymerization degree of M, and n1 ranges from 10to 30; in N n2, N is a styrene monomer, an N-butyl acrylate monomer, methyl acrylate, isooctyl acrylate or methyl methacrylate monomer unit, N2 is the average polymerization degree of N, and the range of N2 is 1-8; the X group is an alkyl dithioester group or an alkyl trithioester group;
(2) Adding 10wt% concentration sodium hydroxide aqua, adding isooctyl acrylate or isooctyl acrylate and methacrylic acid, adding water, adding second initiator at 40-60 deg.c for reaction in anaerobic environment for 3-10 hr, adding hard monomer and reaction in anaerobic environment for 5-10 hr to obtain main matrix polymer latex;
(3) After the reaction, the polymer latex, 30wt% hydrogen peroxide and 7.5wt% hydrochloric acid are mixed according to the volume ratio of 3:2:3, placing the mixture in a beaker, stirring the mixture for 15min until the mixture is uniform, heating the mixture to 50 ℃, and reacting the mixture for 1.5 to 3 hours; washing the precipitate with distilled water to neutrality, air drying, vacuum drying in a vacuum oven at 120deg.C for 5-20 hr to obtain multiblock copolymer;
(4) After the reaction, the polymer latex, 30wt% hydrogen peroxide and 7.5wt% hydrochloric acid are mixed according to the volume ratio of 2:1:2, placing the mixture in a beaker, stirring the mixture for 15min until the mixture is uniform, heating the mixture to 40-60 ℃, and reacting the mixture for 1.5-3h; washing the precipitate with distilled water for several times to neutrality, air drying, vacuum drying in a vacuum oven at 120deg.C for 5-20 hr to obtain reinforced matrix;
(5) And dissolving the multiblock copolymer, tackifying resin and other assistants in a dispersion medium, coating the mixture into a film in an argon environment, and drying the film to finally obtain the OCA optical adhesive.
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