CN115109528A - Method for preparing adhesive product by single-side sizing - Google Patents
Method for preparing adhesive product by single-side sizing Download PDFInfo
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- CN115109528A CN115109528A CN202110304826.7A CN202110304826A CN115109528A CN 115109528 A CN115109528 A CN 115109528A CN 202110304826 A CN202110304826 A CN 202110304826A CN 115109528 A CN115109528 A CN 115109528A
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- substrate
- ethyl ketone
- methyl ethyl
- adhesive
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- 239000000853 adhesive Substances 0.000 title claims abstract description 74
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000004513 sizing Methods 0.000 title claims description 15
- 239000000758 substrate Substances 0.000 claims abstract description 63
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000012459 cleaning agent Substances 0.000 claims abstract description 28
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000002798 polar solvent Substances 0.000 claims abstract description 13
- 239000007822 coupling agent Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 150000004820 halides Chemical class 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 101
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 20
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 150000002513 isocyanates Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000003599 detergent Substances 0.000 claims description 6
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical group ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 229950009390 symclosene Drugs 0.000 claims description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- GGBJHURWWWLEQH-UHFFFAOYSA-N Butyl-cyclohexane Natural products CCCCC1CCCCC1 GGBJHURWWWLEQH-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940116423 propylene glycol diacetate Drugs 0.000 claims description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- NUKZAGXMHTUAFE-UHFFFAOYSA-N hexanoic acid methyl ester Natural products CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 claims description 2
- 238000004026 adhesive bonding Methods 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 20
- 238000012360 testing method Methods 0.000 description 19
- 229920001971 elastomer Polymers 0.000 description 15
- 239000005060 rubber Substances 0.000 description 14
- 239000004814 polyurethane Substances 0.000 description 13
- 229920003009 polyurethane dispersion Polymers 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 239000002649 leather substitute Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- TZZGHGKTHXIOMN-UHFFFAOYSA-N 3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCC[Si](OC)(OC)OC TZZGHGKTHXIOMN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- -1 aminosilane compound Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 150000001718 carbodiimides Chemical group 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000007725 thermal activation Methods 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- HEBTZZBBPUFAFE-UHFFFAOYSA-N 2-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=CC=C1S(=O)(=O)N=C=O HEBTZZBBPUFAFE-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 241001330498 Corsia Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- PWKSKIMOESPYIA-BYPYZUCNSA-N L-N-acetyl-Cysteine Chemical compound CC(=O)N[C@@H](CS)C(O)=O PWKSKIMOESPYIA-BYPYZUCNSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VRRABDXZDGRGPC-UHFFFAOYSA-M sodium;2-(2-aminoethylamino)ethanesulfonate Chemical compound [Na+].NCCNCCS([O-])(=O)=O VRRABDXZDGRGPC-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 210000003371 toe Anatomy 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
Images
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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B9/00—Footwear characterised by the assembling of the individual parts
- A43B9/12—Stuck or cemented footwear
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a method for producing a bonded article by single-sided gluing, to the bonded article produced by this method and to the use of the bonded article in the production of footwear. The method comprises the following steps: a. applying a cleaning agent to at least one surface of a first substrate, drying the surface of the first substrate to which the cleaning agent is applied; b. applying an adhesive to at least one surface of a second substrate, drying the surface of the second substrate to which the adhesive is applied; contacting the first substrate surface treated in step a with the second substrate surface treated in step b to obtain the adhesive article; wherein the cleaning agent comprises a polar solvent and a one-end aminosilane coupling agent; the concentration of the cleaning agent is 0.2% -1.2%; the second substrate is pretreated by a treating agent, the treating agent comprises halide and an organic solvent with polarity more than 2.4, and the concentration of the treating agent is 1-3%. The adhesive article of the present invention has excellent adhesive strength and heat resistance.
Description
Technical Field
The invention relates to a method for preparing a bonded product by single-sided sizing, the bonded product prepared by the method and application of the bonded product in the production of shoes.
Background
The traditional process for bonding shoe materials in the shoe industry is a double-sided sizing process, i.e., the adhesive is applied to either the shoe sole or the midsole sole, and often requires cleaning and priming before the adhesive is applied to the midsole, outsole and upper. For example, CN1235966C discloses a laminate comprising a foamed product layer and a polyolefin material layer, wherein the laminate is bonded by double-sided sizing; CN106316147A discloses an activator, comprising a modified aminosilane and a solvent; the modified aminosilane is prepared by reacting an aminosilane compound with a silane modifier; the silane modifier is one or more of monoepoxide glycidyl ether, diepoxide glycidyl ether and polyepoxide glycidyl ether. The double-sided gluing process has the disadvantages of complex process, low production efficiency and high labor cost, and the shoe making industry hopes to find a simplified shoe making process.
The single-side gluing process reduces the gluing step, saves labor force, improves production efficiency, and can avoid the vamp from being polluted by the adhesive, thereby being popular in the shoe making industry. The difficulty of the single-sided sizing process is the need to find suitable cleaning agents and adhesives.
Hot melt adhesives, which can be applied in single-sided gluing processes, have limited application in the shoe-making industry due to their poor initial performance, high equipment costs, and the like. Attempts have been made in the industry to use aqueous polyurethane dispersion adhesives for single-sided sizing processes.
CN1098154C discloses a process for injection molding a laminate by applying a primer comprising an organic solvent and an ethylene or propylene polymer onto which is grafted an unsaturated carboxylic acid or its anhydride, ester, amide, imide or metal salt to a substrate and injection molding the ethylene or propylene polymer onto the primed substrate. This method is not suitable for the application process.
CN107802056A discloses a method for manufacturing shoes by applying powder glue on single surface. The powder glue adopted by the method comprises common polyurethane resin and polyamide resin, and the mechanical property of the shoe material prepared by single-side gluing is far different from that of the shoe material prepared by double-side gluing.
CN108587495A method for improving anaerobic adhesive performance by treating bonding surface with silane coupling agent, comprising the following steps: mixing and completely dissolving silane coupling agent, copper acetate and ethanol in a mass ratio of 1: 20 to obtain a pretreatment solution; uniformly coating the pretreatment solution on two surfaces to be bonded to obtain a pretreated bonding surface; and uniformly coating the anaerobic adhesive on one of the pre-treated bonding surfaces, and butting and fixing the two pre-treated bonding surfaces.
CN1095399A discloses a polyurethane melt adhesive comprising at least one polyurethane prepolymer obtained from at least one polyisocyanate, especially toluene diisocyanate and/or diphenylmethane diisocyanate, at least one polyalkylene glycol, especially polypropylene glycol, and at least one polyester glycol, preferably two polyester glycols having different glass transition temperatures, in a concentration of more than 10% by weight based on the total weight of the melt adhesive, and, if desired, additives such as resins, especially hydrocarbon resins, and stabilizers, especially toluene sulfonyl isocyanate.
Disclosure of Invention
The invention aims to provide a method for preparing a bonded product by single-sided sizing, the bonded product prepared by the method and application of the bonded product in the production of shoes. The adhesive product prepared by the method has good bonding strength and heat resistance.
The method for preparing the bonding product by single-sided sizing comprises the following steps:
a. applying a cleaning agent to at least one surface of a first substrate, dry applying said cleaning agent
A first substrate surface of the agent;
b. applying an adhesive to at least one surface of a second substrate, the adhesive being applied dry
A second substrate surface of the agent; and
c. contacting the first substrate surface treated in step a with the second substrate surface treated in step b to obtain the adhesive article;
wherein the cleaning agent comprises a polar solventAnd a terminal aminosilane coupling agent; the polar solvent has a boiling point not higher than 135 ℃ and is non-reactive with isocyanate; the terminal aminosilane coupling agent conforms to the general formula Y-R 1 -Si-(CH 3 ) n X 3-n Wherein R is 1 Is alkylene with 1-20 carbon atoms, n is 0 or 1, X is selected from-Cl, CH 3 O-、C 2 H 5 O-、(CH 3 ) 2 CHO-and CH 3 OCH 2 CH 2 O-, Y is selected from-NH 2 and-NHR 2 ，R 2 Is an alkyl group having 1 to 10 carbon atoms; the concentration of the cleaning agent is 0.2% -1.2%; the second substrate is pretreated by a treating agent, the treating agent comprises halide and an organic solvent with polarity more than 2.4, and the concentration of the treating agent is 1-3%.
According to one aspect of the present invention, there is provided an adhesive article prepared according to the method provided herein.
According to a further aspect of the invention there is provided the use of an adhesive article provided according to the invention in the manufacture of footwear.
The bonding product obtained by the single-sided sizing method has the initial bonding strength not less than 3N/mm, the final bonding strength not less than 4.5N/mm, the pull-off distance of the initial heat resistance test not more than 5mm, and the pull-off distance of the final heat resistance test not more than 40 mm. The adhesive product obtained by the method has good adhesive strength and heat resistance, and the product has the characteristics of firm adhesion and difficult degumming at both normal temperature and high temperature.
Detailed Description
The invention provides a method for preparing a bonding product by single-sided sizing, which comprises the following steps: a. applying a cleaning agent to at least one surface of a first substrate, drying the surface of the first substrate to which the cleaning agent is applied; b. applying an adhesive to at least one surface of a second substrate, drying the surface of the second substrate to which the adhesive is applied; contacting the first substrate surface treated in step a with the second substrate surface treated in step b to obtain the adhesive article; wherein the cleaning agent comprises a polar solvent and a one-end aminosilane coupling agent; the polar solvent is boiling pointNot higher than 135 ℃ and non-reactive with isocyanates; the terminal amino silane coupling agent conforms to the general formula Y-R 1 -Si-(CH 3 ) n X 3-n Wherein R is 1 Is alkylene having 1 to 20 carbon atoms, n is 0 or 1, X is selected from-Cl, CH 3 O-、C 2 H 5 O-、(CH 3 ) 2 CHO-and CH 3 OCH 2 CH 2 O-, Y is selected from-NH 2 and-NHR 2 ，R 2 Is an alkyl group having 1 to 10 carbon atoms; the concentration of the cleaning agent is 0.2% -1.2%; the second substrate is pretreated by a treating agent, the treating agent comprises halide and an organic solvent with polarity more than 2.4, and the concentration of the treating agent is 1-3%. The invention also provides the adhesive product prepared by the method and the application of the adhesive product in the production of shoes.
The description of "first" and "second" of the first and second substrates of the present invention is merely for convenience of describing the two substrates, and is not intended to distinguish the order of the substrates.
The first substrate and the second substrate of the present invention may be the same or different.
The step a and the step b are not sequential, and can be performed simultaneously, or the step a is performed first and then the step b is performed, or the step b is performed first and then the step a is performed.
The method of calculating the concentration of the treating agent of the present invention is (mass of halide (g)/mass of treating agent (g)) × 100%.
The concentration of the detergent of the present invention is calculated by (mass (g) of the terminal aminosilane coupling agent/mass (g) of the detergent) x 100%.
The term "isocyanate-non-reactive" as used herein means that it does not contain Zerewitinov active hydrogen. The definition of Zerevitinov active hydrogen can be referred to the Romp chemical dictionary (Romp chemical encyclopedia dictionary), tenth edition, Georg Thieme Verlag Stuttgart, 1996. In general, groups containing zerewitinov active hydrogen include, but are not limited to, hydroxyl, amino, and thiol groups.
Cleaning agent
The concentration of the cleaning agent is preferably 0.3% -1.0%.
The amount of the terminal aminosilane coupling agent is preferably 0.2 wt% to 1.2 wt%, most preferably 0.3 wt% to 1.0 wt%, relative to the total weight of the detergent.
The polar solvent of the present invention refers to a solvent in which the solvent molecule is a polar molecule.
The boiling point of the polar solvent is preferably 35 ℃ to 135 ℃.
The polar solvent is preferably one or more of acetone, methyl ethyl ketone, ethyl acetate or butyl acetate, a mixture of butyl acetate and cyclohexane and methyl ethyl ketone, a mixture of methyl ethyl ketone and propylene glycol diacetate, or a mixture of butyl acetate and methyl ethyl ketone and propylene glycol methyl ether acetate.
The polar solvent is further preferably selected from the group consisting of methyl ethyl ketone, butyl acetate, a mixture of methyl ethyl ketone and ethyl acetate, a mixture of methyl ethyl ketone and butyl acetate, a mixture of methyl ethyl ketone and propylene glycol diacetate, a mixture of acetone and butyl acetate, a mixture of ethyl acetate and butyl acetate and methyl ethyl ketone, a mixture of butyl acetate and cyclohexane and methyl ethyl ketone, and a mixture of butyl acetate and methyl ethyl ketone and propylene glycol methyl ether acetate.
Most preferably, the polar solvent is methyl ethyl ketone.
Said R is 2 Alkyl groups having 1 to 6 carbon atoms are preferred, and alkyl groups having 1 to 4 carbon atoms are most preferred.
The terminal aminosilane coupling agent is preferably one or more of the following: gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and bis- (gamma-trimethoxysilylpropyl) amine.
Most preferably, the cleaner comprises methyl ethyl ketone and an amino silane coupling agent, and the concentration of the cleaner is 0.3% -1.0%.
The cleaning agent does not contain a binder.
The polar solvent and the terminal aminosilane coupling agent in the cleaner may be stored separately or may be premixed and present in solution.
A first substrate
The first substrate is those commonly used in the art, in particular materials that can be used in midsoles, uppers and toes. The first substrate is preferably one or more of the following: polyurethane-based materials and polyvinyl chloride-based materials, most preferably polyurethane-based synthetic leather.
Adhesive agent
The adhesive may be a one-component adhesive, a two-component adhesive or a three-component adhesive as is commonly used in the art.
The binder is preferably one or more of the following: solvent type polyurethane, solvent type polychloroprene rubber, aqueous polyurethane dispersion, aqueous polychloroprene rubber and hot melt type polyurethane, more preferably aqueous polyurethane dispersion, most preferably two-component aqueous polyurethane dispersion.
The two-component aqueous polyurethane dispersion preferably comprises an aqueous polyurethane dispersion and an isocyanate curing agent.
The aqueous polyurethane dispersion is preferably an anionic aqueous polyurethane dispersion.
The solids content of the aqueous polyurethane dispersion is preferably from 40% to 60% by weight, relative to the total weight of the aqueous polyurethane dispersion.
The isocyanate curing agent is preferably a water dispersible isocyanate, most preferably a trimer of an aliphatic isocyanate.
The isocyanate curing agent preferably meets at least one of the following characteristics:
an isocyanate group content of 15% to 25% by weight, relative to the total weight of the isocyanate curing agent;
viscosity of 2000 mPas to 4000 mPas, according to DIN EN ISO 3219: 1994-10 at 23 deg.C for 10s -1 At a shear rate of (c) selecting an MV-DIN rotor measurement;
isocyanate functionality of 2.8 to 3.5; and
the number average molecular weight is 200g/mol to 2000 g/mol.
Second base material
The second substrate is those commonly used in the art, in particular rubber-like materials that can be used in shoe uppers, shoe midsoles.
The second substrate is preferably one or more of: natural rubber and synthetic rubber. The synthetic rubber is preferably one or more of the following: nitrile rubber, TPU, TPR, and polyvinyl chloride based materials.
The second substrate is pretreated with a treating agent prior to application of the adhesive.
The organic solvent with polarity greater than 2.4 in the treating agent is preferably one or more of the following: ethyl acetate, butyl acetate, butanone, and acetone.
The halide is preferably trichloroisocyanuric acid.
Most preferably, the treating agent comprises trichloroisocyanuric acid and ethyl acetate, and the treating agent concentration is 1% to 3%.
The pretreatment preferably applies the treatment agent to at least one surface of the second substrate and dries.
The second substrate may also be sanded or cleaned prior to application of the adhesive.
The polishing is used to increase the surface roughness of the substrate. The grinding may be mechanical grinding.
The cleaning is the removal of oil or dirt from the surface of the substrate using solvents, which are well known to those skilled in the art.
Application of
The application may be to apply the cleaning agent or adhesive to the entire surface of the substrate or only to one or more portions of the surface of the substrate.
The application can be brushing, dipping, spraying, rolling, knife coating, flow coating, pouring, printing or transfer printing, preferably brushing, dipping or spraying.
Drying
The drying of the first substrate surface to which the cleaning agent is applied and the drying of the second substrate surface to which the adhesive is applied may refer to drying only the substrate surface, or may refer to drying a part of or the whole of the substrate including the substrate surface to which the cleaning agent or the adhesive is applied.
The drying may remove volatile components. The volatile component may be water.
The drying is preferably one or more of the following: infrared thermal radiation, near infrared thermal radiation, microwaves and the use of convection ovens or spray dryers at elevated temperatures.
The temperature of the drying should not be above the temperature limit at which the substrate deforms in an uncontrolled manner or suffers other damage.
Contact with
Preferably, before the step c, the surface of the second substrate applied with the adhesive, which is treated by the step b, is thermally activated, and the thermal activation temperature is 45 ℃ to 75 ℃.
The thermal activation may be oven activation or infrared activation.
The contact is preferably performed before the temperature of the surface of the second substrate is lowered below the temperature at which the adhesive can adhere, and more preferably before the temperature of the surface of the second substrate is not lower than 60 ℃.
The first substrate is not treated with an adhesive prior to contacting the second substrate.
Adhesive article
The initial bond strength of the adhesive article is preferably not less than 3N/mm, most preferably from 3N/mm to 5.5N/mm.
The final bond strength of the adhesive article is preferably not less than 4.5N/mm, most preferably from 4.5N/mm to 7.0N/mm.
The adhesive article preferably has an initial heat resistance test pull-off distance of no greater than 5mm, most preferably from 1mm to 5 mm.
The adhesive article preferably has a pull-off distance of no greater than 40mm, most preferably from 0mm to 37mm for final heat resistance testing.
The adhesive article is preferably footwear.
Drawings
The invention will be described and explained in more detail below with reference to the drawings, in which:
fig. 1 is a schematic illustration of sample bonding.
FIG. 2 is a schematic diagram of a sample heat resistance test.
Examples
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event that a definition of a term in this specification conflicts with a meaning commonly understood by those skilled in the art to which the invention pertains, the definition set forth herein shall govern.
Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that can vary depending upon the desired properties to be obtained.
As used herein, "and/or" means one or all of the referenced elements.
The use of "including" and "comprising" herein encompasses the presence of the stated elements alone and the presence of other elements not stated in addition to the stated elements.
All percentages in the present invention are by weight unless otherwise indicated.
The analytical measurements according to the invention were carried out at 23. + -. 2 ℃ unless otherwise stated.
Raw materials and reagents
Silquest A-1100: gamma-aminopropyltrimethoxysilane, available from mayform, china ltd.
Silquest A-1120: n-beta- (aminoethyl) gamma-aminopropyltrimethoxysilane, available from Meiji China, Inc.
Silquest A-1170: bis (gamma-trimethoxysilylpropyl) amine, available from mai-ji, china ltd.
Silquest A-1524: gamma- (biuret) propyltrimethoxysilane, available from mai-ji, ltd.
Silquest A-link 25: gamma- (isocyanato) propyltriethoxysilane, available from mayform, china ltd.
Desmocoll 526: polyurethane resins, available from scientific Limited.
Dispercoll U54: the anionic aqueous polyurethane dispersion has a solid content of 50 +/-1% and can be purchased from Corsai Limited.
Polyester I: 1, 4-butanediol polyadipate diol having an OH number of 50.
Polyester II: polyester diols composed of 1, 6-hexanediol, neopentyl glycol and adipic acid, with OH numbers of 66.
Dispercoll U58/1: the anionic aqueous polyurethane dispersion has a solid content of 50+ 1% and is available from Corcisco Ltd.
Desmodur XP 2802: 40% by weight of a solid, hydrophilically modified polycarbodiimide, having a melting point of 23.16 ℃ in the solid component, a carbodiimide functional group content of 1mmol/g, a number average molecular weight of 1779, a weight average molecular weight of 3258 and a carbodiimide functional group of 4.5, commercially available from Corsai Limited.
Bayhydur XP 2655: an HDI-based aliphatic trimer having an NCO group content of 20.8% by weight, a viscosity of approximately 3500 mPas (23 ℃ C.), a solids content of 100% by weight, an isocyanate functionality of 3.2 and a number average molecular weight of 700g/mol, commercially available from Corcisco Ltd.
MEK: methyl ethyl ketone, available from Yonghua chemical technology (Jiangsu) Ltd.
Black rubber: sole rubber made of nitrile rubber is available from Dongguan Wantai rubber Co., Ltd.
L-10: the PU synthetic leather is commercially available from Anhui Anli synthetic leather Co., Ltd.
L-27A: the PU synthetic leather is commercially available from Anhui Anli synthetic leather Co., Ltd.
L-35: the PU synthetic leather is commercially available from Anhui Anli synthetic leather Co., Ltd.
Borchigel L75N: thickener, available from OMG.
Preparation of adhesive 1
99.2g of Dispercoll U58/1 and 0.8g of 25% strength Borchigel L75N were mixed to a viscosity of approximately 5000 mPas, stirred for 10 minutes, then 5g of Bayhydur XP 2655 were added and stirring was continued for 10 minutes to give adhesive 1.
Preparation of adhesive 2
450g of polyester I and 42.5g of polyester II are dehydrated at 110 ℃ and 100mbar for 1 hour, 2.25g of 1, 4-butanediol are added and the mixture is cooled while stirring. 37.84g of the solution was added thereto at 60 ℃
H, followed by addition of 25g
I, the mixture is stirred at 80 to 90 ℃ until an isocyanate content of 1.3% is reached. The reaction mixture was dissolved in 840g of acetone and cooled to 50 ℃. After a solution of 5.6g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 2.4g diethanolamine and 0.8g hydroxyethylethylenediamine in 656g water was added to the reaction mixture solution and stirred vigorously for 30 minutes, the mixture was dispersed by adding 510g water, followed by distilling off the acetone to obtain an aqueous polyurethane dispersion. 100g of the above aqueous polyurethaneurea dispersion was mixed with 2g of Desmodur XP2802 at 1000rpm with stirring for 10-15 minutes, then 1g of Borchigel L75N with 25% solids was added to mix to a viscosity of about 5000 mPas, after 10 minutes stirring 5g of Bayhydur XP 2655 was added and stirring was continued for 10 minutes to give adhesive 2.
Substrates of examples and comparative examples
The components were mixed in the amounts shown in Table 1, and manually stirred for 5-10 minutes to obtain a detergent. The surface of the PU synthetic leather (first substrate) (2 cm wide and 8 cm long) to be bonded was washed with fibers containing a detergent, gently scrubbed several times, and then dried in an oven at a temperature of 60 ℃ for 3 minutes, for use.
A polished black rubber (second substrate) (2 cm wide and 8 cm long) surface to be bonded was washed with a fiber cloth or yarn containing methyl ethyl ketone, the washed black rubber surface was exposed to a fume hood until the washed surface was dried, a treatment agent shown in Table 1 (treatment agent 1 comprising trichloroisocyanuric acid and ethyl acetate, treatment agent 1 concentration of 2%; treatment agent 2 comprising Silquest A-1170 and methyl ethyl ketone, treatment agent 2 concentration of 1%) was painted on the surface, followed by drying in an oven at a temperature of 60 ℃ for 3 minutes, and then an adhesive shown in Table 1 was painted on the black rubber surface with a fine brush in an amount of 120g/m 2 (wet). Finally, the black rubber surface applied with the adhesive is dried in a circulating air furnace at 60 ℃ until the moisture in the adhesive film is completely removed for standby.
Bond Strength test
The surface of the black rubber ready for use was heated to 60 ℃, and then the black rubber was quickly attached to the PU synthetic leather ready for use using a flat press (gory, china) at a pressure of 4bar as shown in fig. 1, and maintained for 30 seconds to obtain a sample of an adhesive article.
The samples were tested for their adhesive strength according to DIN EN 1392 using a tensile machine from ZWICK, model BZ2.5/TN 1S. The non-bonded parts of the black rubber and the PU synthetic leather are respectively clamped between an upper clamp and a lower clamp of a tensile machine, the bonding surface of the black rubber and the PU synthetic leather is tested to present a 180-degree stripping mode under the conditions that the stretching speed is 100mm/min and the stretching length is 50mm, the tensile force used at the time is recorded as the bonding strength, and the results are listed in table 1. The initial bond strength (measured 30 minutes after application) should not be less than 3N/mm and the final bond strength (measured 24 hours after application) should not be less than 4.5N/mm. The greater the bond strength obtained from the test indicates a greater bond between the substrates and a stronger bond between the substrates.
Heat resistance test
The surface of the black rubber ready for use was heated to 60 ℃, and then the black rubber and the PU synthetic leather ready for use were quickly attached at a pressure of 4bar using a flat press (gory, china), as shown in fig. 1, and maintained for 10 seconds to obtain a sample of an adhesive article.
Initial heat resistance test: the sample was allowed to stand at ambient temperature for 2 minutes and then held at 80 ℃ for 30 minutes with a 500g weight, and the pull-off distance of the sample after 30 minutes at 80 ℃ was recorded as shown in fig. 2, and the time to come to full open for the coating was recorded if the coating could not be maintained for 30 minutes, i.e. come to full open for degumming, and the results are shown in table 1. The pull-off distance is the length of separation of the sample attachment site measured with a graduated scale. The longer the pull-apart distance, the poorer the heat resistance of the sample. And the full degumming opening refers to that the joint parts of the sample are completely separated, and the sample is not subjected to the heat resistance test if the full degumming opening is performed. The pull-apart distance should be no more than 5 mm.
Final heat resistance test: the sample was allowed to stand at ambient temperature for 24 hours and then a 1000g weight was loaded at 80 ℃ and held for 30 minutes as shown in fig. 2, and the pull-off distance of the sample after being held at 80 ℃ for 30 minutes was recorded, and if the coating could not be held for 30 minutes, i.e. the coating was degummed and fully opened, the time for the coating to degummed and fully opened was recorded, and the results are shown in table 1. The pull-off distance is the length of separation of the sample application site measured with a graduated scale. The longer the pull-apart distance, the poorer the heat resistance of the sample. The degumming full opening refers to that the joint parts of the sample are completely separated, and the degumming full opening refers to that the sample does not pass the heat resistance test. The pull-apart distance should be no greater than 40 mm.
Examples 1 to 9 and comparative examples 1 to 12
Table 1 lists the results of the bond strength and heat resistance tests for samples of the treating agents, components of the cleaning agents, and adhesive articles of examples 1-9 and comparative examples 1-12.
TABLE 1 test results of subdivided and bonded article samples of examples and comparative examples
As can be seen from examples 1-9, the single-sided sizing method of the present invention provided bonded articles having an initial bond strength of not less than 3N/mm, a final bond strength of not less than 4.5N/mm, an initial heat resistance test pull-off distance of not more than 5mm, and a final heat resistance test pull-off distance of not more than 40mm, and the bonded articles provided by the method of the present invention all had good bond strength and heat resistance.
As can be seen from comparative examples 1-3 and examples 1-7, the single-side sizing process results in bonded articles having good bond strength and heat resistance when the cleaner concentration is between 0.2% and 1.2% and a suitable terminal aminosilane coupling agent is selected. The cleaner of comparative example 1 contained only methyl ethyl ketone, and the adhesive article obtained by the method of comparative example 1 was delaminated and fully opened at 5 minutes in the initial heat resistance test and at 9 minutes in the final heat resistance test, and the adhesive article was poor in heat resistance. The concentration of the cleaning agent of comparative example 2 was 0.1%, and the adhesive article obtained by the method of comparative example 2 was debonded and fully opened at 12 minutes in the initial heat resistance test and debonded and fully opened at 18 minutes in the final heat resistance test, and the heat resistance of the adhesive article was poor. The concentration of the cleaner of comparative example 3 was 1.5%, and the adhesive article obtained by the method of comparative example 3 had an initial bond strength of 2.9N/mm and a final bond strength of 3.9N/mm, which was lower than the bond strength requirement and the article had poor bond strength.
As can be seen from comparative examples 4 to 7, the cleaning agents of the comparative examples contain γ - (biuret) propyltrimethoxysilane or γ - (isocyanate) propyltriethoxysilane, and the adhesive articles of the comparative examples cannot achieve both adhesive strength and heat resistance.
The cleaning agent used in the single-sided sizing method of comparative examples 8 to 9 was methyl ethyl ketone, and the adhesive articles prepared therefrom were inferior in initial heat resistance and final heat resistance to the adhesive articles of examples 8 to 9 of the present invention, respectively.
As can be seen from comparative examples 10 to 11, the cleaning agents of the comparative examples contained Desmocoll 526 or Dispercoll U54, and the adhesive articles of the comparative examples were poor in initial heat resistance and final heat resistance.
As can be seen from comparative example 12, when the treating agent comprises Silquest A-1170 and methyl ethyl ketone, the adhesive strength and heat resistance of the article of comparative example are poor.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing description, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description; and therefore any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (11)
1. A method for preparing a bonded article by single-sided sizing, comprising the steps of:
a. applying a cleaning agent to at least one surface of a first substrate, drying the surface of the first substrate to which the cleaning agent is applied;
b. applying an adhesive to at least one surface of a second substrate, drying the surface of the second substrate to which the adhesive is applied; and
c. contacting the first substrate surface treated in step a with the second substrate surface treated in step b to obtain the adhesive article;
wherein the cleaning agent comprises a polar solvent and a one-end aminosilane coupling agent; the polar solvent has a boiling point not higher than 135 ℃ and is non-reactive with isocyanate; the terminal aminosilane coupling agent conforms to the general formula Y-R 1 -Si-(CH 3 ) n X 3-n Wherein R is 1 Is alkylene with 1-20 carbon atoms, n is 0 or 1, X is selected from-Cl, CH 3 O-、C 2 H 5 O-、(CH 3 ) 2 CHO-and CH 3 OCH 2 CH 2 O-, Y is selected from-NH 2 and-NHR 2 ，R 2 Is an alkyl group having 1 to 10 carbon atoms; the concentration of the cleaning agent is 0.2% -1.2%; the secondThe substrate is pretreated with a treating agent comprising a halide and an organic solvent having a polarity greater than 2.4, the treating agent being present at a concentration of 1% to 3%.
2. The method of claim 1, wherein the polar solvent is one or more of acetone, methyl ethyl ketone, ethyl acetate, or butyl acetate, a mixture of butyl acetate and cyclohexane and methyl ethyl ketone, a mixture of methyl ethyl ketone and propylene glycol diacetate, a mixture of butyl acetate and methyl ethyl ketone and propylene glycol methyl ether acetate; it is further preferred to select from methyl ethyl ketone, butyl acetate, a mixture of methyl ethyl ketone and ethyl acetate, a mixture of methyl ethyl ketone and butyl acetate, a mixture of methyl ethyl ketone and propylene glycol diacetate, a mixture of acetone and butyl acetate, a mixture of ethyl acetate and butyl acetate and methyl ethyl ketone, a mixture of butyl acetate and cyclohexane and methyl ethyl ketone, a mixture of butyl acetate and methyl ethyl ketone and propylene glycol methyl ether acetate, most preferably methyl ethyl ketone.
3. The method of claim 1 or 2, wherein R is 2 Is an alkyl group having 1 to 6 carbon atoms, most preferably an alkyl group having 1 to 4 carbon atoms.
4. The method of any of claims 1-3, wherein the terminal aminosilane coupling agent is one or more of: gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and bis- (gamma-trimethoxysilylpropyl) amine.
5. The method of any of claims 1-4, wherein the detergent concentration is 0.3% to 1.0%.
6. The method of any of claims 1-5, wherein the cleaner comprises methyl ethyl ketone and an amino silane coupling agent, and the cleaner concentration is from 0.3% to 1.0%.
7. The method of any one of claims 1-6, wherein the organic solvent having a polarity greater than 2.4 is one or more of: ethyl acetate, butyl acetate, butanone, and acetone.
8. The method of any one of claims 1-7, wherein the halide is trichloroisocyanuric acid.
9. The method of any one of claims 1-8, wherein the treating agent comprises trichloroisocyanuric acid and ethyl acetate, and the treating agent concentration is from 1% to 3%.
10. An adhesive article made according to the method of any one of claims 1-9.
11. Use of an adhesive article according to claim 10 in the production of footwear.
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| CN202110304826.7A CN115109528A (en) | 2021-03-22 | 2021-03-22 | Method for preparing adhesive product by single-side sizing |
| PCT/EP2022/057106 WO2022200199A1 (en) | 2021-03-22 | 2022-03-18 | Method for preparing an adhered article by conducting single-sided gluing |
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| CN111746074A (en) * | 2019-03-29 | 2020-10-09 | 科思创德国股份有限公司 | Method for preparing adhesive product by single-side sizing |
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| CN111746074A (en) * | 2019-03-29 | 2020-10-09 | 科思创德国股份有限公司 | Method for preparing adhesive product by single-side sizing |
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