CN116554791A - Anti-yellowing high-adhesion OCA optical adhesive and preparation method thereof - Google Patents
Anti-yellowing high-adhesion OCA optical adhesive and preparation method thereof Download PDFInfo
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- CN116554791A CN116554791A CN202310490542.0A CN202310490542A CN116554791A CN 116554791 A CN116554791 A CN 116554791A CN 202310490542 A CN202310490542 A CN 202310490542A CN 116554791 A CN116554791 A CN 116554791A
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- 230000003287 optical effect Effects 0.000 title claims abstract description 76
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 75
- 239000000853 adhesive Substances 0.000 title claims abstract description 73
- 238000004383 yellowing Methods 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 20
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004513 sizing Methods 0.000 claims abstract description 16
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims abstract description 13
- -1 acrylic ester Chemical class 0.000 claims abstract description 12
- 239000004840 adhesive resin Substances 0.000 claims abstract description 11
- 229920006223 adhesive resin Polymers 0.000 claims abstract description 11
- 239000003085 diluting agent Substances 0.000 claims abstract description 11
- NDXLVXDHVHWYFR-UHFFFAOYSA-N 2-pyridin-1-ium-1-ylacetohydrazide;chloride Chemical compound [Cl-].NNC(=O)C[N+]1=CC=CC=C1 NDXLVXDHVHWYFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012782 phase change material Substances 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- FSGAMPVWQZPGJF-UHFFFAOYSA-N 2-methylbutan-2-yl ethaneperoxoate Chemical compound CCC(C)(C)OOC(C)=O FSGAMPVWQZPGJF-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 11
- 239000000194 fatty acid Substances 0.000 claims description 11
- 229930195729 fatty acid Natural products 0.000 claims description 11
- 150000004665 fatty acids Chemical class 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 239000003094 microcapsule Substances 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000005022 packaging material Substances 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 2
- 239000004568 cement Substances 0.000 abstract description 15
- 239000000084 colloidal system Substances 0.000 abstract description 2
- 238000005187 foaming Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- 238000011056 performance test Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 235000019864 coconut oil Nutrition 0.000 description 3
- 239000003240 coconut oil Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229940079826 hydrogen sulfite Drugs 0.000 description 3
- SYOYTIYFEGZNHN-UHFFFAOYSA-N pentyl ethaneperoxoate Chemical group CCCCCOOC(C)=O SYOYTIYFEGZNHN-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 2
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229920001800 Shellac Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- PXICJHCWSGDEQB-UHFFFAOYSA-M sodium;prop-2-enoate;sulfurous acid Chemical compound [Na+].OS([O-])=O.OC(=O)C=C PXICJHCWSGDEQB-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Classifications
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
Abstract
The application relates to the technical field of optical cement, and particularly discloses yellowing-resistant high-adhesion OCA optical cement and a preparation method thereof. The yellowing-resistant high-adhesion OCA optical adhesive comprises the following raw materials in parts by weight: 80-140 parts of acrylic acid, 20-50 parts of acrylic ester, 40-100 parts of diluent, 32-78 parts of viscous resin telomer, 12-28 parts of hydroquinone monomethyl ether, 10-30 parts of transparent phase-change particles and 3-9 parts of Girard reagent P; wherein the adhesive resin telomer raw material comprises 2-18 parts of sodium bisulphite and 30-60 parts of acrylic resin. The preparation method comprises the following steps: s1, preparing an initial mixed sizing material; s2, preparing a viscous resin telomer; s3, preparing the yellowing-resistant high-adhesion OCA optical adhesive. The optical adhesive prepared in the application has good yellowing resistance and strong cohesiveness, is not easy to cause phenomena such as degumming, foaming or yellowing of colloid, and can keep high transparency for a long time.
Description
Technical Field
The application relates to the technical field of optical cement materials, in particular to yellowing-resistant high-adhesion OCA optical cement and a preparation method thereof.
Background
The optical adhesive is a special adhesive for bonding transparent optical elements, the adhesive needs to be colorless and transparent, has good bonding performance, maintains stable properties after being cured, and has light transmittance of more than ninety percent. The existing optical adhesive is divided into organic silica gel, acrylic resin, other polyester such as polyurethane, epoxy resin and other adhesives, and the optical adhesive of the type can be widely applied to the fields of mobile phone manufacturing industry, electronic industry and the like and has wide application prospect, but most of optical adhesives need to solve the problem of yellowing under the conditions of high temperature, ultraviolet rays and the like.
In the related art, the tackiness of the acrylic resin adhesive is superior to other types of adhesives, but such adhesives require polymerization inhibition of acrylic acid by using a polymerization inhibitor, thereby inhibiting adverse phenomena such as yellowing and shrinkage caused by polymerization reaction; the polymerization inhibitor has certain timeliness and limitation, yellowing can still occur due to the failure of the polymerization inhibitor region after the use time, and the addition of the polymerization inhibitor is excessive and also weakens the action of the viscous component, so that the yellowing resistance and the adhesive property of the optical adhesive are required to be further improved, and the service life of the optical adhesive is prolonged.
Disclosure of Invention
In order to alleviate phenomena of yellowing, shrinkage or loss of cohesiveness of optical adhesives under conditions of ultraviolet rays, peroxides, overheated environments and the like, the application provides a yellowing-resistant high-cohesiveness OCA optical adhesive and a preparation method thereof.
In a first aspect, the application provides a yellowing-resistant high-adhesion OCA optical adhesive, which adopts the following technical scheme:
the yellowing-resistant high-adhesion OCA optical adhesive comprises the following raw materials in parts by weight: 80-140 parts of acrylic acid, 20-50 parts of acrylic ester, 40-100 parts of diluent, 33-81 parts of viscous resin telomer, 12-28 parts of hydroquinone monomethyl ether, 10-30 parts of transparent phase-change particles and 3-9 parts of Girard reagent P;
wherein the raw materials of the adhesive resin telomer comprise 2-18 parts of sodium bisulphite, 1-3 parts of initiator and 30-60 parts of acrylic resin.
By adopting the technical scheme, the acrylic acid resin and the sodium bisulphite are adopted to react to generate the sodium bisulphite acrylic acid telomer, so that the viscosity of the optical cement material can be obviously enhanced, the effects of improving the transparency and resisting oxidation are achieved, and the yellowing phenomenon of the optical cement is slowed down. The hydroquinone monomethyl ether is used as a polymerization inhibitor to prevent a large amount of self-polymerization phenomenon of monomer acrylic acid in the optical adhesive, and the self-polyacrylic acid has the advantages of crisp texture, poor toughness, poor dimensional stability, easy aging and poor long-term heat-resistant stability, and can reduce the relevant performance of the optical adhesive.
Preferably, the adhesive resin telomer raw material further comprises 20-50 parts by weight of fir resin gum or lac resin.
By adopting the technical scheme, the antioxidation capability and the adhesive property of the optical adhesive can be obviously improved by adopting the natural resin with strong adhesive force such as fir resin adhesive or lac resin.
Preferably, the transparent phase-change particles are phase-change particles made of transparent phase-change materials wrapped by transparent wrapping materials, and the particle size is smaller than 50nm.
Preferably, the acrylic ester is obtained by mixing methyl methacrylate, propylene glycol methyl ether acetate and tert-amyl peroxyacetate which are added in a weight ratio of 1 (1-4) to 2-3.
By adopting the technical scheme, the mechanical property and yellowing resistance of the three acrylic esters can be improved through copolymerization after mixing, and the mechanical property and yellowing resistance of the three acrylic esters are better than those of the acrylic esters in all aspects, and the addition of the tert-amyl peroxyacetate can further deepen the acceleration degree of the copolymerization process, save the time cost and obtain better positive effects.
Preferably, the transparent packaging material comprises one or more of epoxy resin, silica gel and transparent plastic; the transparent phase change material comprises any three or more of polyethylene glycol, paraffin, fatty acid and crystalline hydrated salt, and the weight adding ratio of the transparent packing material to the transparent phase change material is (2-5) to (3-6).
By adopting the technical scheme, the filling phase change material compounded by three or more phase change materials has better temperature control effect, the effective temperature control range can cover larger temperature change range, and the acrylic acid series components in the optical adhesive are effectively prevented from self-polymerizing and greatly delaying the oxidation of the optical adhesive by the addition of the polymerization inhibitor through the good temperature control effect, so that the yellowing resistance of the optical adhesive is remarkably improved.
Preferably, the preparation method of the phase-change particles comprises the following steps: firstly, carrying out gradient heating and air bubble exhausting operation on a transparent phase-change material, firstly heating to 88-92 ℃ and preserving heat for 10-20min, then heating to 120-130 ℃ and preserving heat for 10-20min, finally rapidly cooling and solidifying, crushing the transparent phase-change material to obtain phase-change material powder, and wrapping the phase-change material powder with a transparent wrapping material by adopting a spray drying method to obtain the transparent phase-change microcapsule.
In a second aspect, the present application provides a preparation method of a yellowing-resistant high-adhesion OCA optical adhesive, which adopts the following technical scheme:
a preparation method of yellowing-resistant high-adhesion OCA optical adhesive comprises the following steps:
s1, preparing an initial mixed sizing material: mixing acrylic resin and transparent phase change particles, and uniformly stirring to obtain a primary mixed sizing material;
s2, preparing a viscous resin telomer: mixing sodium bisulphite and acrylic resin, heating to 160-170 ℃ in vacuum, adding an initiator, reacting for 30-90min, and obtaining a viscous resin telomer after the reaction is finished;
s3, preparing yellowing-resistant high-adhesion OCA optical adhesive: adding the mixed hydroquinone monomethyl ether, the diluent, the Girad reagent P and the viscous resin telomer into the primary mixed sizing material, and reducing the stirring rotation speed and uniformly stirring to obtain the yellowing-resistant high-adhesion OCA optical adhesive.
Preferably, in the step of preparing the adhesive resin telomer, when sodium bisulphite and acrylic resin are mixed and heated in vacuum, 20-50 parts by weight of fir resin gum or lac resin is also added for heating.
Preferably, in the step S3, the diluent is ethanol.
In summary, the present application has the following beneficial effects:
1. because the acrylic acid and sodium bisulphite are adopted to react to generate the sodium bisulphite acrylic telomer, the viscosity of the colloid can be greatly enhanced, the effects of improving transparency and resisting oxidation are achieved, and the yellowing phenomenon of the optical adhesive is slowed down. The hydroquinone monomethyl ether is used as a polymerization inhibitor to prevent a great deal of self-polymerization phenomenon of monomer acrylic acid in the optical adhesive, and the self-polyacrylic acid has the advantages of relatively poor impact resistance, relatively brittleness, poor toughness, poor dimensional stability, easy aging, poor long-term heat resistance stability, capability of reducing the performance of the optical adhesive, good comprehensive performance, high strength and toughness, good heat resistance, good dimensional stability, excellent low-temperature toughness, high transparency and relatively good luster of the surface.
2. The fir resin adhesive and the telomer are preferably added to have better synergistic tackifying effect, meanwhile, the phase change material capable of preserving heat and insulating heat is added, the stability of the temperature of the optical adhesive material is maintained when the environmental temperature changes greatly, the influence of heating and heating of equipment on acrylic acid in the adhesive material in application scenes such as mobile phones or other electronic products on promotion of self-polymerization reaction is avoided, and therefore the effect of improving yellowing resistance is achieved.
Detailed Description
The present application is further described in detail with reference to the following examples, which are specifically described: the following examples, in which no specific conditions are noted, are conducted under conventional conditions or conditions recommended by the manufacturer, and the raw materials used in the following examples are commercially available from ordinary sources except for the specific descriptions.
The initiator in the application is tert-amyl peroxyacetate produced by Hubei Chengfeng chemical Co Ltd;
the diluent in the application is ethanol produced by Shandong Taixi chemical industry Co.
Preparation example of transparent phase-change particles
Preparation example 1
The preparation method of the transparent phase-change particles comprises the following steps: heating and mixing 10kg of polyethylene glycol-6000, 10kg of fatty acid and 10kg of crystalline hydrated salt to obtain a transparent phase-change material, carrying out gradient heating and air-bubble exhausting operation on the transparent phase-change material, firstly heating to 88 ℃ and preserving heat for 20min, then heating to 120 ℃ and preserving heat for 20min, finally rapidly cooling and solidifying, reducing the temperature to 4 ℃, smashing the solidified transparent phase-change material, and wrapping the smashed transparent phase-change material with 20kg of epoxy resin by adopting a spray drying method according to the weight adding ratio of epoxy resin to the transparent phase-change material of 2:3 to obtain the transparent phase-change microcapsule; wherein the epoxy resin is bisphenol A type standard liquid medium viscosity epoxy resin YD-128; the fatty acid is coconut oil fatty acid; the crystalline hydrated salt is 5kg of sodium thiosulfate pentahydrate hydrated salt and 5kg of sodium acetate trihydrate hydrated salt.
Preparation example 2
The preparation method of the transparent phase-change particles comprises the following steps: heating and mixing 10kg of polyethylene glycol-6000, 10kg of fatty acid and 10kg of paraffin to obtain a transparent phase-change material, carrying out gradient heating and air-discharging bubble operation on the transparent phase-change material, firstly heating to 90 ℃ and preserving heat for 15min, then heating to 125 ℃ and preserving heat for 15min, finally rapidly cooling and solidifying, reducing the temperature to 4 ℃, smashing the solidified transparent phase-change material, and wrapping the smashed transparent phase-change material with 50kg of molten polyethylene by adopting a spray drying method according to the weight adding ratio of polyethylene to the transparent phase-change material of 5:3 to obtain the transparent phase-change microcapsule; wherein the polyethylene is linear low density polyethylene; the fatty acid is coconut oil fatty acid.
Preparation example 3
The preparation method of the transparent phase-change particles comprises the following steps: heating and mixing 10kg of crystalline hydrated salt, 10kg of fatty acid and 20kg of paraffin to obtain a transparent phase-change material, carrying out gradient heating and air-discharging bubble operation on the transparent phase-change material, firstly heating to 92 ℃ and preserving heat for 10min, then heating to 130 ℃ and preserving heat for 10min, finally rapidly cooling and solidifying, reducing the temperature to 4 ℃, smashing the solidified transparent phase-change material, and wrapping the smashed transparent phase-change material with 20kg of transparent silica gel by adopting a spray drying method according to the weight adding ratio of the transparent silica gel to the transparent phase-change material of 1:3 to obtain the transparent phase-change microcapsule; the transparent silica gel is HY301 LED high-transparency silica gel; the fatty acid is coconut oil fatty acid; the crystalline hydrated salt is 5kg of sodium thiosulfate pentahydrate hydrated salt and 5kg of sodium acetate trihydrate hydrated salt.
Preparation example 4
The procedure of preparation 1 was followed except that no step-wise elevated temperature bubble operation was performed, heating directly to 120 degrees celsius, and then cooling and solidifying.
Preparation example 5
The procedure of preparation 1 was followed except that the crystalline hydrated salt was replaced with polyethylene glycol-6000 in equal amounts, i.e., particles were filled with only two phase change materials.
Anti-yellowing high-adhesion optical adhesive embodiment
Example 1
The yellowing-resistant high-adhesion OCA optical adhesive comprises the following raw materials: 80kg of acrylic acid, 20kg of acrylic acid ester, 40kg of ethanol, 33kg of viscous resin telomer, 12kg of hydroquinone monomethyl ether, 10kg of transparent phase-change particles prepared in preparation example 1, and 3kg of Girad reagent P; the tackifying resin telomer raw material comprises 2kg of sodium bisulfite, 1kg of tertiary amyl peroxyacetate and 30kg of acrylic resin; wherein, the acrylic ester is prepared by mixing methyl methacrylate, propylene glycol methyl ether acetate and tert-amyl peroxyacetate which are added according to the weight ratio of 1:1:2.
A preparation method of yellowing-resistant high-adhesion OCA optical adhesive comprises the following steps:
s1, preparing an initial mixed sizing material: mixing acrylic resin and transparent phase change particles, and uniformly stirring to obtain a primary mixed sizing material;
s2, preparing a viscous resin telomer: mixing hydrogen sulfite and acrylic resin, heating to 60 ℃ in vacuum, adding tert-amyl peroxyacetate, and reacting for 90min to obtain a viscous resin telomer after the reaction is finished;
s3, preparing yellowing-resistant high-adhesion OCA optical adhesive: adding the mixed hydroquinone monomethyl ether, the diluent, the Girad reagent P and the viscous resin telomer into the primary mixed sizing material, and reducing the stirring rotation speed and uniformly stirring to obtain the yellowing-resistant high-adhesion OCA optical adhesive.
Example 2
The yellowing-resistant high-adhesion OCA optical adhesive comprises the following raw materials: 110kg of acrylic acid, 35kg of acrylic acid ester, 70kg of ethanol, 55kg of viscous resin telomer, 20kg of hydroquinone monomethyl ether, 20kg of transparent phase-change particles prepared in preparation example 2 and 6 parts of Girad reagent P; the tackifying resin telomer raw material comprises 5kg of sodium bisulphite, 2kg of tertiary amyl peroxyacetate and 48kg of acrylic resin; wherein, the acrylic ester is methyl methacrylate, propylene glycol methyl ether acetate and tert-amyl peroxyacetate which are added according to the weight ratio of 1:2.5:2.5.
A preparation method of yellowing-resistant high-adhesion OCA optical adhesive comprises the following steps:
s1, preparing an initial mixed sizing material: mixing acrylic resin and transparent phase change particles, and uniformly stirring to obtain a primary mixed sizing material;
s2, preparing a viscous resin telomer: mixing hydrogen sulfite and acrylic resin, heating to 65 ℃ in vacuum, adding tert-amyl peroxyacetate, reacting for 60min, and obtaining a viscous resin telomer after the reaction is finished;
s3, preparing yellowing-resistant high-adhesion OCA optical adhesive: adding the mixed hydroquinone monomethyl ether, the diluent, the Girad reagent P and the viscous resin telomer into the primary mixed sizing material, and reducing the stirring rotation speed and uniformly stirring to obtain the yellowing-resistant high-adhesion OCA optical adhesive.
Example 3
The yellowing-resistant high-adhesion OCA optical adhesive comprises the following raw materials: 140kg of acrylic acid, 50kg of acrylic acid ester, 100kg of ethanol, 78kg of viscous resin telomer, 28kg of hydroquinone monomethyl ether, 30kg of transparent phase-change particles prepared in preparation example 3, and 9kg of Girad reagent P; the tackifying resin telomer raw material comprises 8kg of sodium bisulfite, 3kg of tertiary amyl peroxyacetate and 67kg of acrylic resin; wherein, the acrylic ester is prepared by mixing methyl methacrylate, propylene glycol methyl ether acetate and tert-amyl peroxyacetate which are added according to the weight ratio of 1:4:3.
A preparation method of yellowing-resistant high-adhesion OCA optical adhesive comprises the following steps:
s1, preparing an initial mixed sizing material: mixing acrylic resin and transparent phase change particles, and uniformly stirring to obtain a primary mixed sizing material;
s2, preparing a viscous resin telomer: mixing hydrogen sulfite and acrylic resin, heating to 60 ℃ in vacuum, adding tert-amyl peroxyacetate, and reacting for 30min to obtain a viscous resin telomer after the reaction is finished;
s3, preparing yellowing-resistant high-adhesion OCA optical adhesive: adding the mixed hydroquinone monomethyl ether, the diluent, the Girad reagent P and the viscous resin telomer into the primary mixed sizing material, and reducing the stirring rotation speed and uniformly stirring to obtain the yellowing-resistant high-adhesion OCA optical adhesive.
Example 4
The procedure of example 1 was followed except that the propylene glycol methyl ether acetate in the feed was replaced with methyl methacrylate in equal amounts.
Example 5
The procedure of example 1 was followed except that 50 parts of fir resin gum was added during the temperature increase in the preparation of the adhesive resin telomer.
Example 6
The procedure of example 1 was followed, except that the transparent phase-change material was not subjected to the operation of temperature-rising and bubble-discharging during the preparation of the transparent phase-change particles, i.e., the transparent phase-change particles prepared in preparation example 1 were replaced with the transparent phase-change particles prepared in preparation example 4 in equal amounts.
Example 7
The procedure of example 1 was followed except that the t-amyl peroxyacetate in the feed was replaced by propylene glycol methyl ether acetate in equal amounts.
Example 8
The procedure of example 1 was followed, except that the transparent phase-change particles prepared in preparation example 1 were replaced with the transparent phase-change particles prepared in preparation example 5 in equal amounts.
Example 9
The procedure of example 1 was followed except that 20 parts of shellac resin was added during the elevated temperature of the preparation of the viscous resin telomer.
Comparative example
Comparative example 1
The procedure of example 1 was followed except that no tackifying resin telomer was added to the starting material.
Comparative example 2
The procedure of example 1 was followed except that hydroquinone monomethyl ether was not added to the starting material.
Comparative example 3
The procedure of example 1 was followed except that no Girard reagent P was added to the starting materials.
Comparative example 4
The procedure of example 1 was followed, except that no transparent phase change particles were added to the starting material.
Comparative example 5
The procedure of example 1 was followed except that sodium bisulphite was not added to the tackifying resin telomer stock.
Performance test
1. Optical adhesive adhesion test
2. Optical cement yellowing resistance test
Detection method
1. Optical cement adhesion test: according to the GB/T4851-1998 test standard, the effective adhesion area of a mirror-finished special 304 metal plate is 25mm by 25mm, the test weight is 1kg, the adhesion conditions of comparative examples of each example are recorded at 500h, 1000h and 2000h respectively, the shrinkage rate of the cured optical adhesive is recorded, and the peel strength of the comparative examples of each example is recorded, and the detection results are shown in Table 1.
2. And (3) testing yellowing resistance of the optical adhesive: with 340nm UV irradiation at an illuminance of 0.76 w/(m) 2 Nm) the optical cement prepared in each comparative example was subjected to yellowing b-value test at 240h and 960h, respectively, the temperature was maintained in the range of 30-50 degrees celsius, and the original transmittance test was performed using YH1200 haze meter (universal type) for each comparative example, and the detection results are shown in table 2.
Table 1:
table 2:
as can be seen from the performance test results of examples 1 and 4, the equivalent amount of propylene glycol methyl ether acetate in the raw materials is replaced by methyl methacrylate, the peel strength index of the copolymer produced by the reaction is obviously defective when a single acrylic ester is used, shrinkage is generated after the optical cement is cured, and the effect of improving the shrinkage resistance of the optical cement by copolymerization of various acrylic esters such as propylene glycol methyl ether acetate is better and the peel strength can be increased.
As can be seen from the performance test results of examples 1 and 5, when the fir resin gum raw material was added during the preparation of the adhesive resin telomer, the oxidation resistance of the adhesive resin telomer was improved, the yellowing was delayed, and the bonding effect was good.
As can be seen from the performance test results of example 1 and example 6, when the transparent phase change material is not subjected to the operations of high temperature bubble removal and vacuum storage during the preparation of the transparent phase change particles, a large number of micro bubbles exist, so that the light transmittance of the optical cement material is reduced.
As can be seen from the performance test results of examples 1 and 7, when the tert-amyl peroxyacetate in the raw materials was replaced with propylene glycol methyl ether acetate in equal amounts, the reaction rate was slow, the reaction degree was low, and some of the raw materials were not copolymerized, so that good dimensional stability and gum toughness could not be obtained.
As can be seen from the performance test results of examples 1 and 8, when the transparent phase-change particles prepared in preparation example 1 were replaced with the transparent phase-change particles prepared in preparation example 5, the temperature control performance of the phase-change material was reduced, and the effect of the polymerization inhibitor was limited when the ultraviolet absorption temperature was increased, and a part of the acrylic acid was self-polymerized and easily oxidized and yellow-changed, so that the yellowing resistance and the adhesive performance of the optical adhesive were reduced with the oxidation of the adhesive material.
As can be seen from the results of the performance test in combination with example 1 and comparative example 1, there was a significant decrease in the adhesive performance of the optical adhesive without the addition of the tackifying resin telomer.
As can be seen from the performance test results of the example 1 and the comparative example 2, when hydroquinone monomethyl ether is not added in the raw materials, a large amount of acrylic acid self-polymers are generated and are easy to oxidize and yellow, so that the oxidation resistance and the yellowing resistance of the optical adhesive are greatly reduced.
As can be seen from the performance test results of the example 1 and the comparative example 3, the raw materials have a synergistic effect without adding the Girad reagent P and hydroquinone monomethyl ether, and a small amount of acrylic acid is generated from a polymer to generate yellowing when the Girad reagent P is not added, so that the oxidation resistance and yellowing resistance of the optical adhesive are slightly reduced.
As can be seen from the performance test results of example 1 and comparative example 4, when transparent phase change particles are not added in the raw materials, the temperature of the prepared optical cement material changes with the increase of the environment, the optical cement material has no adjustment capability, the temperature increase causes the optical cement material to perform uncontrollable self-polymerization and copolymerization reaction, and a polymer which is easy to yellow is generated, so that the yellowing resistance is reduced, the oxidation resistance is reduced, and the time for maintaining effective cohesiveness is reduced.
As can be seen from the results of the performance test in combination with example 1 and comparative example 5, it is different in that when sodium bisulphite is not added to the raw material of the adhesive resin telomer, no reaction occurs to form telomer, and thus yellowing resistance cannot be improved, and adhesiveness is slightly improved but the amplitude is not obvious.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (9)
1. The yellowing-resistant high-adhesion OCA optical adhesive is characterized by comprising the following raw materials in parts by weight: 80-140 parts of acrylic acid, 20-50 parts of acrylic ester, 40-100 parts of diluent, 33-81 parts of viscous resin telomer, 12-28 parts of hydroquinone monomethyl ether, 10-30 parts of transparent phase-change particles and 3-9 parts of Girard reagent P;
wherein the raw materials of the adhesive resin telomer comprise 2-18 parts of sodium bisulphite, 1-3 parts of initiator and 30-60 parts of acrylic resin.
2. The yellowing-resistant high-adhesion OCA optical adhesive of claim 1, wherein: the adhesive resin telomer raw material also comprises 20-50 parts by weight of fir resin glue or lac resin.
3. The yellowing-resistant high-adhesion OCA optical adhesive of claim 1, wherein: the transparent phase-change particles are phase-change particles made of transparent phase-change materials wrapped by transparent wrapping materials, and the particle size is smaller than 50nm.
4. The yellowing-resistant high-adhesion OCA optical adhesive of claim 1, wherein: the acrylic ester is obtained by mixing methyl methacrylate, propylene glycol methyl ether acetate and tert-amyl peroxyacetate which are added in a weight ratio of 1 (1-4) to 2-3.
5. A yellowing-resistant high-adhesion OCA optical adhesive according to claim 3, wherein: the transparent packaging material comprises one or more of epoxy resin, silica gel and transparent plastic; the transparent phase change material comprises any three or more of polyethylene glycol, paraffin, fatty acid and crystalline hydrated salt, and the weight adding ratio of the transparent packing material to the transparent phase change material is (2-5) to (3-6).
6. The yellowing-resistant high-adhesion OCA optical adhesive according to claim 3, wherein the preparation method of the phase-change particles comprises the following steps: firstly, carrying out gradient heating and air bubble exhausting operation on a transparent phase-change material, firstly heating to 88-92 ℃ and preserving heat for 10-20min, then heating to 120-130 ℃ and preserving heat for 10-20min, finally rapidly cooling and solidifying, crushing the transparent phase-change material to obtain phase-change material powder, and wrapping the phase-change material powder with a transparent wrapping material by adopting a spray drying method to obtain the transparent phase-change microcapsule.
7. The method for preparing the yellowing-resistant high-adhesion OCA optical adhesive according to any one of claims 1 to 6, comprising the following steps:
s1, preparing an initial mixed sizing material: mixing acrylic resin and transparent phase change particles, and uniformly stirring to obtain a primary mixed sizing material;
s2, preparing a viscous resin telomer: mixing sodium bisulphite and acrylic resin, heating to 160-170 ℃ in vacuum, adding an initiator, reacting for 30-90min, and obtaining a viscous resin telomer after the reaction is finished;
s3, preparing yellowing-resistant high-adhesion OCA optical adhesive: adding the mixed hydroquinone monomethyl ether, the diluent, the Girad reagent P and the viscous resin telomer into the primary mixed sizing material, and reducing the stirring rotation speed and uniformly stirring to obtain the yellowing-resistant high-adhesion OCA optical adhesive.
8. The method for preparing the yellowing-resistant high-adhesion OCA optical adhesive, which is characterized in that: in the step of preparing the adhesive resin telomer, when sodium bisulphite and acrylic resin are mixed and heated in vacuum, 20-50 parts by weight of fir resin glue or lac resin is also added for heating.
9. The method for preparing the yellowing-resistant high-adhesion OCA optical adhesive, which is characterized in that: the diluent in the step S3 is ethanol.
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| US20080119626A1 (en) * | 2005-04-07 | 2008-05-22 | Hirotama Fujimaru | Polyacrylic Acid (Salt) Water-Absorbent Resin, Production Process Thereof, and Acrylic Acid Used in Polymerization for Production of Water-Absorbent Resin |
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