CN118126659A - Pressure-sensitive adhesive, preparation method thereof and pressure-sensitive adhesive product - Google Patents
Pressure-sensitive adhesive, preparation method thereof and pressure-sensitive adhesive product Download PDFInfo
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- CN118126659A CN118126659A CN202410546669.4A CN202410546669A CN118126659A CN 118126659 A CN118126659 A CN 118126659A CN 202410546669 A CN202410546669 A CN 202410546669A CN 118126659 A CN118126659 A CN 118126659A
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- pressure
- sensitive adhesive
- acrylate
- polyacrylate
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 57
- 239000004814 polyurethane Substances 0.000 claims abstract description 51
- 229920002635 polyurethane Polymers 0.000 claims abstract description 51
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 39
- -1 acrylic ester Chemical class 0.000 claims abstract description 32
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 19
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- 239000003085 diluting agent Substances 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 12
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 claims abstract description 5
- IQJVBAIESAQUKR-UHFFFAOYSA-N isocyanic acid;prop-2-enoic acid Chemical compound N=C=O.OC(=O)C=C IQJVBAIESAQUKR-UHFFFAOYSA-N 0.000 claims abstract description 4
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical compound [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 claims description 15
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 150000003505 terpenes Chemical class 0.000 claims description 6
- 235000007586 terpenes Nutrition 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- CQUTXCKGINHWKG-UHFFFAOYSA-N isocyanato prop-2-enoate Chemical compound C=CC(=O)ON=C=O CQUTXCKGINHWKG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002313 adhesive film Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000002349 favourable effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 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 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 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 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a pressure-sensitive adhesive, a preparation method thereof and a pressure-sensitive adhesive product. The pressure-sensitive adhesive comprises the following raw materials: 70% -90% of polyacrylate, 1% -5% of tackifying resin, 0.1% -1% of cross-linking agent and 5% -25% of first solvent; the raw materials of the polyacrylate comprise: 25% -45% of soft monomer, 5% -20% of hard monomer, 0.5% -3.5% of functional monomer, 0.5% -3.5% of organosilicon modified polyurethane acrylate, 0.01% -1% of initiator and 40% -50% of second solvent; the raw materials of the organosilicon modified polyurethane acrylic ester comprise: 5% -10% of polyisocyanate, 0.5% -2% of isocyanate silane coupling agent, 65% -80% of polyester polyol, 8% -15% of isocyanate acrylate, 2% -8% of diluent and 0.01% -0.1% of polymerization inhibitor. The pressure-sensitive adhesive has good adhesive property.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a pressure-sensitive adhesive, a preparation method thereof and a pressure-sensitive adhesive product.
Background
Pressure-sensitive adhesives are of great relevance to our production and life because of the variety of pressure-sensitive adhesives available for different uses, such as rubber-type pressure-sensitive adhesives, polyurethane pressure-sensitive adhesives, acrylate pressure-sensitive adhesives, and the like. The acrylic acid ester pressure-sensitive adhesive has various advantages, such as good coating adaptability and weather resistance, can freely adjust viscosity and peeling strength, can be prepared into light-cured and thermosetting pressure-sensitive adhesives, and has the most wide application range. Although the conventional acrylic pressure-sensitive adhesive has excellent peel strength, the effect is not ideal when some metal oxide layers are bonded, for example, the peel force on aluminum oxide formed on the surface of pure aluminum is much smaller than that on stainless steel plates.
Disclosure of Invention
Based on this, it is necessary to provide a pressure-sensitive adhesive, a method for producing the same and a pressure-sensitive adhesive article, aiming at the problem of how to enhance the adhesive property.
The pressure-sensitive adhesive comprises the following raw materials in percentage by mass:
70% -90% of polyacrylate;
1% -5% of tackifying resin;
0.1% -1% of cross-linking agent; and
5% -25% Of a first solvent;
wherein, the raw materials for preparing the polyacrylate comprise the following components in percentage by mass:
25% -45% of soft monomer;
5% -20% of hard monomer;
0.5% -3.5% of functional monomer;
0.5% -3.5% of organosilicon modified polyurethane acrylic ester;
0.01% -1% of an initiator; and
40% -50% Of a second solvent;
wherein, the raw materials for preparing the organosilicon modified polyurethane acrylic ester comprise the following components in percentage by mass:
5% -10% of polyisocyanate;
0.5% -2% of isocyanate silane coupling agent;
65% -80% of polyester polyol;
8% -15% of isocyanate acrylate;
2% -8% of a diluent; and
0.01% -0.1% Of polymerization inhibitor.
According to the pressure-sensitive adhesive, polyisocyanate, an isocyanato silane coupling agent and polyester polyol are subjected to polymerization reaction according to the raw material combination to obtain a polyurethane intermediate with hydroxyl as a terminal group, and then the polyurethane intermediate is reacted with isocyanato acrylic ester to obtain organosilicon modified polyurethane acrylic ester; polymerizing the organosilicon modified polyurethane acrylic ester with the monomers to obtain polyacrylate; the polyacrylate is combined with the components, and a polyurethane chain segment and a silane coupling agent chain segment are introduced, so that the pressure-sensitive adhesive with excellent adhesive force is obtained. The combination of the components and the percentage ranges of the components are determined through a large number of experiments, and the combination and the percentage ranges of the components enable the pressure-sensitive adhesive to have good adhesive property and are favorable for wide application.
In one possible implementation, the polyisocyanate is selected from at least one of MDI, TDI and IPDI;
The isocyanatosilane coupling agent is at least one of 3-isocyanatopropyl trimethoxysilane and 3-isocyanatopropyl triethoxysilane;
The isocyanate group acrylic ester is isocyanate group ethyl acrylate.
In one possible implementation, the soft monomer is selected from at least one of n-butyl acrylate and isooctyl acrylate;
The hard monomer is at least one selected from styrene, vinyl acetate and methyl (meth) acrylate;
The functional monomer is at least one selected from (methyl) acrylic acid, (methyl) acrylamide and hydroxyethyl (methyl) acrylate.
In one possible implementation, the tackifying resin is selected from at least one of rosin resins, petroleum resins, terpene resins, alkyl phenolic resins, and terpene phenolic resins.
In one possible implementation, the polymerization inhibitor is selected from at least one of hydroquinone and p-benzoquinone;
the cross-linking agent is a polyfunctional isocyanate curing agent;
the initiator is at least one selected from azodiisobutyronitrile and benzoyl peroxide.
In one possible implementation, the first solvent and the second solvent are independently selected from at least one of ethyl acetate, toluene, butyl acetate, acetone, and methyl ethyl ketone;
the diluent is (meth) acrylic acid.
The preparation method of the pressure-sensitive adhesive comprises the following steps:
uniformly mixing polyisocyanate, an isocyanato silane coupling agent, polyester polyol and a polymerization inhibitor, then fully reacting at the temperature of 75-80 ℃, then adding isocyanato acrylate, then fully reacting at the temperature of 75-80 ℃ until the NCO content is less than 0.5%, cooling, then adding a diluent, and fully uniformly mixing to obtain organosilicon modified polyurethane acrylate;
Uniformly mixing the organosilicon modified polyurethane acrylic ester, the soft monomer, the hard monomer, the functional monomer, the initiator and the second solvent, and fully reacting at the temperature of 70-75 ℃ to obtain polyacrylate; and
And uniformly mixing the polyacrylate, the tackifying resin, the cross-linking agent and the first solvent, and defoaming to obtain the pressure-sensitive adhesive.
According to the preparation method of the pressure-sensitive adhesive, polyisocyanate, an isocyanato silane coupling agent and polyester polyol are subjected to polymerization reaction to obtain a polyurethane intermediate with hydroxyl end groups, and then the polyurethane intermediate is reacted with isocyanato acrylic ester to obtain organosilicon modified polyurethane acrylic ester; polymerizing the organosilicon modified polyurethane acrylic ester with the monomers to obtain polyacrylate; the polyacrylate is combined with the components, and the polyurethane chain segment and the silane coupling agent chain segment are introduced, so that the pressure-sensitive adhesive with excellent adhesive force is obtained, and the pressure-sensitive adhesive has good adhesive property and is favorable for wide application.
In one possible implementation, after the polyisocyanate, the isocyanato silane coupling agent, the polyester polyol and the polymerization inhibitor are uniformly mixed and fully reacted, the molar ratio of hydroxyl groups to isocyanate groups is (1.8-2.0): 1.
A pressure-sensitive adhesive article comprising the pressure-sensitive adhesive of any of the above.
In the pressure-sensitive adhesive product of the technical scheme, the pressure-sensitive adhesive has good adhesive property, so that the 180-degree peel strength of the pressure-sensitive adhesive product is higher, and the pressure-sensitive adhesive product is favorable for wide application.
In one possible implementation, the pressure-sensitive adhesive article is a pressure-sensitive adhesive tape or film.
Drawings
FIG. 1 is a flow chart of a method for preparing a pressure sensitive adhesive according to an embodiment of the present invention.
Detailed Description
The following detailed description of the present invention will provide further details in order to make the above-mentioned objects, features and advantages of the present invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
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. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The pressure-sensitive adhesive of an embodiment comprises the following raw materials in percentage by mass:
70% -90% of polyacrylate;
1% -5% of tackifying resin;
0.1% -1% of cross-linking agent; and
5% -25% Of a first solvent;
Wherein, the raw materials for preparing the polyacrylate comprise the following components in percentage by mass:
25% -45% of soft monomer;
5% -20% of hard monomer;
0.5% -3.5% of functional monomer;
0.5% -3.5% of organosilicon modified polyurethane acrylic ester;
0.01% -1% of an initiator; and
40% -50% Of a second solvent;
wherein, the raw materials for preparing the organosilicon modified polyurethane acrylic ester comprise the following components in percentage by mass:
5% -10% of polyisocyanate;
0.5% -2% of isocyanate silane coupling agent;
65% -80% of polyester polyol;
8% -15% of isocyanate acrylate;
2% -8% of a diluent; and
0.01% -0.1% Of polymerization inhibitor.
In the pressure-sensitive adhesive of the above embodiment, in the raw material for preparing the organosilicon modified urethane acrylate, polyisocyanate, an isocyanato silane coupling agent and polyester polyol are subjected to polymerization reaction to obtain a polyurethane intermediate with hydroxyl as a terminal group, and then the polyurethane intermediate is reacted with the isocyanato acrylate to obtain the organosilicon modified urethane acrylate. Further, the polyester polyol is preferably a liquid polyester polyol such as Baycoll@AV2113, which is easy to handle and has good adhesion.
In the raw materials for preparing the polyacrylate, the soft monomer, the hard monomer and the functional monomer are taken together as monomers, and the polyacrylate is obtained after the monomers are polymerized with the organosilicon modified polyurethane acrylate, so that the excellent balance of mechanical properties such as initial adhesion, 180-degree peel strength, holding adhesion and the like of the pressure-sensitive adhesive is facilitated.
Among the raw materials for preparing the pressure-sensitive adhesive, the tackifying resin is beneficial to improving the adhesiveness of the material; the crosslinking agent can react with carboxyl or hydroxyl groups in the polyacrylate, and the crosslinking agent is preferably a normal-temperature curing agent. The polyacrylate is combined with the components, and a polyurethane chain segment and a silane coupling agent chain segment are introduced, so that the pressure-sensitive adhesive with excellent adhesive force is obtained.
In the pressure-sensitive adhesive of the above embodiment, the combination of these components and the above percentage ranges of the respective components are determined by a large number of experiments, and the combination and the percentage ranges by mass make the pressure-sensitive adhesive of the present embodiment have good adhesive properties, which is advantageous for wide application.
On the basis of the foregoing embodiment, the polyisocyanate is at least one selected from MDI (chinese name diphenylmethane diisocyanate), TDI (chinese name toluene diisocyanate) and IPDI (chinese name isophorone diisocyanate).
On the basis of the foregoing embodiment, the isocyanatosilane coupling agent is selected from at least one of 3-isocyanatopropyl trimethoxysilane and 3-isocyanatopropyl triethoxysilane.
In addition to the foregoing embodiments, the isocyanate-based acrylate is isocyanate-based ethyl acrylate.
On the basis of the foregoing embodiment, the soft monomer is selected from at least one of n-butyl acrylate and isooctyl acrylate; the hard monomer is at least one selected from styrene, vinyl acetate and methyl (meth) acrylate; the functional monomer is at least one selected from (methyl) acrylic acid, (methyl) acrylamide and (methyl) hydroxyethyl acrylate. Among them, the soft monomer is the most important monomer among the acrylic esters, and its function is to produce a polymer having a low glass transition temperature (Tg) and an initial tackiness. The hard monomer in turn can give a higher glass transition temperature and can copolymerize with the soft monomer. After the hard monomer and the soft monomer are copolymerized according to the proper proportion, the pressure-sensitive adhesive with higher cohesive strength and better service temperature performance can be prepared. The functional monomer is an vinyl monomer with various functional groups and can be copolymerized with soft monomers and hard monomers, so that the pressure-sensitive adhesive can generate a certain degree of crosslinking, and the cohesive strength, the heat resistance and the better holding power are improved.
In addition to the foregoing embodiments, the tackifying resin is selected from at least one of rosin resins, petroleum resins, terpene resins, alkyl phenolic resins, and terpene phenolic resins.
In addition to the foregoing embodiments, the polymerization inhibitor is at least one selected from hydroquinone and p-benzoquinone. These types of polymerization inhibitors have a good effect of preventing self-polymerization.
In addition to the foregoing embodiments, the crosslinking agent is a polyfunctional isocyanate curing agent. The crosslinking agent is further preferably a room temperature curing agent, which may be, but not limited to, colorgina L-75, etc., for the purpose of increasing the crosslinking density and increasing the cohesive strength.
On the basis of the foregoing embodiment, the initiator is selected from at least one of Azobisisobutyronitrile (AIBN) and benzoyl peroxide. These types of radical initiators are capable of generating radicals by thermal decomposition to initiate polymerization of the monomers.
In addition to the foregoing embodiments, the first solvent and the second solvent are independently selected from at least one of ethyl acetate, toluene, butyl acetate, acetone, and methyl ethyl ketone. The first solvent is used as a diluent for controlling viscosity, and the solvents of the types are selected to facilitate coating; the second solvent is preferably ethyl acetate or toluene, which is favorable for the synthesis of polyacrylate.
In addition to the foregoing embodiments, the diluent is (meth) acrylic acid.
According to the pressure-sensitive adhesive, polyisocyanate, an isocyanato silane coupling agent and polyester polyol are subjected to polymerization reaction according to the raw material combination to obtain a polyurethane intermediate with hydroxyl as a terminal group, and then the polyurethane intermediate is reacted with isocyanato acrylic ester to obtain organosilicon modified polyurethane acrylic ester; polymerizing the organosilicon modified polyurethane acrylic ester with the monomers to obtain polyacrylate; the polyacrylate is combined with the components, and a polyurethane chain segment and a silane coupling agent chain segment are introduced, so that the pressure-sensitive adhesive with excellent adhesive force is obtained. The combination of the components and the percentage ranges of the components are determined through a large number of experiments, and the combination and the percentage ranges of the components enable the pressure-sensitive adhesive to have good adhesive property and are favorable for wide application.
Referring to fig. 1, a method for preparing a pressure-sensitive adhesive according to an embodiment of the present invention is characterized by comprising the following steps:
s10, uniformly mixing polyisocyanate, an isocyanato silane coupling agent, polyester polyol and a polymerization inhibitor, then fully reacting at the temperature of 75-80 ℃, then adding isocyanato acrylate, then fully reacting at the temperature of 75-80 ℃ until the NCO content is less than 0.5%, cooling, then adding a diluent, and fully and uniformly mixing to obtain the organosilicon modified polyurethane acrylate.
In step S10, the polyester polyol is preferably a liquid polyester polyol, and may be dehydrated before use, and the liquid polyester polyol is operated as follows: adding the liquid polyester polyol into a dry and impurity-free reaction bottle, heating the material to 120 ℃ while stirring, vacuumizing and stirring for 1-3 h under the pressure of-0.1 MPa, discharging, and placing in a drying room for standby.
In the step S10, polyisocyanate, an isocyanato silane coupling agent and polyester polyol are subjected to polymerization reaction to obtain a polyurethane intermediate with hydroxyl as a terminal group, and then the polyurethane intermediate is reacted with isocyanato acrylate to obtain the organosilicon modified polyurethane acrylate. The specific reaction equation is as follows:
a. The reaction equation for synthesizing the polyurethane intermediate with hydroxyl at one end is as follows:
(I) ; or alternatively
（II）。
B. synthesizing an organosilicon modified polyurethane acrylate monomer, wherein the reaction equation is as follows:
(III); or alternatively
（IV）。
Wherein R represents a polyester group; r 1 represents a structure other than NCO groups in the diisocyanate; r 2 represents- (CH 2)3-Si(OCH3)3) or- (CH 2)3-Si(OCH2CH3)3).
In one possible implementation, after the polyisocyanate, the isocyanato silane coupling agent, the polyester polyol and the polymerization inhibitor are uniformly mixed and fully reacted, the molar ratio of hydroxyl groups to isocyanate groups is (1.8-2.0): 1.
And S20, uniformly mixing the organosilicon modified polyurethane acrylic ester, the soft monomer, the hard monomer, the functional monomer, the initiator and the second solvent, and fully reacting at the temperature of 70-75 ℃ to obtain the polyacrylate.
In the step S20, the organosilicon modified polyurethane acrylic ester, the soft monomer, the hard monomer and the functional monomer are subjected to solution polymerization to obtain the polyacrylate.
And S30, uniformly mixing the polyacrylate, the tackifying resin, the cross-linking agent and the first solvent obtained in the step S20, and defoaming to obtain the pressure-sensitive adhesive.
In step S30, the tackifying resin is beneficial to improving the material viscosity; the crosslinking agent is capable of reacting with carboxyl or hydroxyl groups in the polyacrylate.
According to the preparation method of the pressure-sensitive adhesive, polyisocyanate, an isocyanato silane coupling agent and polyester polyol are subjected to polymerization reaction to obtain a polyurethane intermediate with hydroxyl end groups, and then the polyurethane intermediate is reacted with isocyanato acrylic ester to obtain organosilicon modified polyurethane acrylic ester; polymerizing the organosilicon modified polyurethane acrylic ester with the monomers to obtain polyacrylate; the polyacrylate is combined with the components, and the polyurethane chain segment and the silane coupling agent chain segment are introduced, so that the pressure-sensitive adhesive with excellent adhesive force is obtained, and the pressure-sensitive adhesive has good adhesive property and is favorable for wide application.
An embodiment of the pressure sensitive adhesive article comprises any of the pressure sensitive adhesives described above.
On the basis of the foregoing embodiment, the pressure-sensitive adhesive article is a pressure-sensitive adhesive tape or film.
The pressure-sensitive adhesive tape can be prepared by the following steps: coating the prepared pressure-sensitive adhesive on a PET (polyethylene terephthalate) base film, controlling the thickness of the coated dry adhesive to be 10-50 microns, drying for 5-10 min at 95-125 ℃, covering a fluorine release film, and curing for 72h at 50 ℃ to obtain the pressure-sensitive adhesive tape.
The pressure-sensitive adhesive film can be prepared by the following steps: and coating the prepared pressure-sensitive adhesive on a fluorine release film, controlling the thickness of the coated dry adhesive to be 10-50 microns, drying at 95-125 ℃ for 5-10 min, covering the fluorine release film with different release forces, and curing at 50 ℃ for 72h to obtain the pressure-sensitive adhesive film.
In the pressure-sensitive adhesive product of the technical scheme, the pressure-sensitive adhesive has good adhesive property, so that the 180-degree peel strength of the pressure-sensitive adhesive product is higher, and the pressure-sensitive adhesive product is favorable for wide application.
With reference to the foregoing embodiments, in order to make the technical solution of the present invention more specific, clear and easy to understand, the technical solution of the present invention will be illustrated, but it should be noted that the content to be protected by the present invention is not limited to the following embodiments 1 to 3.
Example 1
Example 1 provides a pressure sensitive adhesive, the raw material components and mass are shown in table 1 (a), table 1 (b) and table 1 (c).
Table 1 (a) Silicone-modified urethane acrylate (A1)
In table 1 (a), n (OH)/N (NCO) =1.885; the theoretical value of NCO content is 0%, and the actual measurement is 0.22%.
TABLE 1 (B) polyacrylate (B1)
TABLE 1 (C) acrylic pressure sensitive adhesive (C1)
Example 2
Example 2 provides a pressure sensitive adhesive, the raw material components and mass are shown in table 2 (a), table 2 (b) and table 2 (c).
Table 2 (a) Silicone-modified urethane acrylate (A2)
In table 2 (a), n (OH)/N (NCO) =1.974; the theoretical value of NCO content is 0%, and the actual measurement is 0.31%.
TABLE 2 (B) polyacrylate (B2)
TABLE 2 (C) acrylate pressure sensitive adhesive (C2)
Example 3
Example 3 provides a pressure sensitive adhesive, the raw material components and mass are shown in Table 3 (a), table 3 (b) and Table 3 (c).
Table 3 (a) Silicone-modified urethane acrylate (A3)
In table 3 (a), n (OH)/N (NCO) =1.998; the theoretical value of NCO content is 0%, and the actual measurement is 0.25%.
TABLE 3 (B) polyacrylate (B3)
TABLE 3 (C) acrylate pressure sensitive adhesive (C3)
Comparative example 1
Comparative example 1 provides an acrylate pressure sensitive adhesive, the raw material components and mass are detailed in tables 4 (a) and 4 (b).
Table 4 (a) polyacrylate (B4)
TABLE 4 (b) acrylate pressure sensitive adhesive (C4)
Comparative example 2
Comparative example 2 provides an acrylate pressure sensitive adhesive, the raw material components and mass are detailed in tables 5 (a) and 5 (b).
Table 5 (a) polyacrylate (B5)
TABLE 5 (b) acrylate pressure sensitive adhesive (C5)
Comparative example 3
Comparative example 3 provides an acrylate pressure sensitive adhesive, the raw material components and mass are detailed in tables 6 (a) and 6 (b).
TABLE 6 (a) polyacrylates (B6)
TABLE 6 (b) acrylate pressure sensitive adhesive (C6)
The pressure-sensitive adhesives of examples 1 to 3 and comparative examples 1 to 3 were prepared as follows:
Weighing raw materials according to the raw material formulation tables of examples 1-3 and comparative examples 1-3, and sequentially synthesizing organosilicon modified polyurethane acrylate, polyacrylate and pressure-sensitive adhesive according to the following steps;
① Synthesis of organosilicon modified polyurethane acrylate
A. Dehydration of liquid polyester polyols
Adding the liquid polyester polyol into a dry reaction bottle without impurities, heating the material to 120 ℃ while stirring, vacuumizing and stirring for 2 hours under the pressure of-0.1 MPa, discharging, and placing in a drying room for standby.
B. Adding diisocyanate, an isocyanate silane coupling agent and a polymerization inhibitor into a dry impurity-free reaction bottle provided with a thermometer, a stirrer and a condenser tube, starting condensed water, and heating the materials to 75 ℃; adding liquid polyester polyol into a reaction bottle, controlling the temperature of the material at 75-80 ℃ during the period, preserving heat for reaction for 3 hours, directly adding isocyanate-based acrylic ester, preserving heat for 3 hours at 75-80 ℃, measuring the NCO content to be less than 0.5% (the theoretical value at the moment is recorded as the NCO content theoretical value), then stirring the material while cooling to be less than 35 ℃, adding a diluent, stirring for 30 minutes, discharging for standby, and marking as the organosilicon modified polyurethane acrylic ester A.
② Synthesis of polyacrylates
Adding soft monomer, hard monomer, functional monomer, organosilicon modified polyurethane acrylic ester A, initiator and second solvent into a dry impurity-free reaction bottle provided with a thermometer, a stirrer, a condenser and a dropwise adding device, starting stirring and condensing water, gradually heating the material to 70 ℃, preserving heat at 70-75 ℃, reacting for 5 hours, detecting the solid content, cooling to below 35 ℃ after the solid content is qualified (the solid content is more than 48%), discharging for standby, and marking as polyacrylate B.
③ Preparation of pressure sensitive adhesive
And uniformly stirring the polyacrylate B, the tackifying resin, the crosslinking agent and the first solvent, and defoaming to obtain the pressure-sensitive adhesive C.
Performance test:
the pressure-sensitive adhesive tapes made of the pressure-sensitive adhesives synthesized in examples 1 to 3 and comparative examples 1 to 3 were subjected to 180-degree peel strength test as follows:
(1) Coating the pressure-sensitive adhesive of examples 1-3 and comparative examples 1-3 on a PET base film with the thickness of 50 microns to prepare a tape with the thickness of 50 microns, drying and covering a PET fluorine release film (release force of 3 g-8 g) for curing to obtain a pressure-sensitive adhesive tape to be tested;
(2) The pressure-sensitive adhesive tape was pretreated (test piece was not polished) according to the method of GB/T2792-1998, and then adhered to a pure aluminum substrate which was not polished (pure aluminum was not protected by a coating), and a set (5 pieces each, the test results were averaged) of peel strength in N/25mm was made to obtain the data in Table 7.
TABLE 7 test results of pressure-sensitive adhesives of examples 1-3 and comparative examples 1-3
As can be seen from the test results of Table 7, comparative examples 1, 2 and 3 are acrylate pressure-sensitive adhesives which were not synthesized with polyurethane segments and silane coupling agents, and the peel strength thereof was lower on the unground pure aluminum substrates than in examples 1, 2 and 3, which illustrate that the present invention can improve the adhesion by synthesizing the silicone-modified polyurethane acrylate, and thus have higher peel strength, indicating that the pressure-sensitive adhesives of the present invention have good adhesive properties.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The pressure-sensitive adhesive is characterized by comprising the following raw materials in percentage by mass:
70% -90% of polyacrylate;
1% -5% of tackifying resin;
0.1% -1% of cross-linking agent; and
5% -25% Of a first solvent;
wherein, the raw materials for preparing the polyacrylate comprise the following components in percentage by mass:
25% -45% of soft monomer;
5% -20% of hard monomer;
0.5% -3.5% of functional monomer;
0.5% -3.5% of organosilicon modified polyurethane acrylic ester;
0.01% -1% of an initiator; and
40% -50% Of a second solvent;
wherein, the raw materials for preparing the organosilicon modified polyurethane acrylic ester comprise the following components in percentage by mass:
5% -10% of polyisocyanate;
0.5% -2% of isocyanate silane coupling agent;
65% -80% of polyester polyol;
8% -15% of isocyanate acrylate;
2% -8% of a diluent; and
0.01% -0.1% Of polymerization inhibitor.
2. The pressure sensitive adhesive of claim 1, wherein the polyisocyanate is selected from at least one of MDI, TDI, and IPDI;
The isocyanatosilane coupling agent is at least one of 3-isocyanatopropyl trimethoxysilane and 3-isocyanatopropyl triethoxysilane;
The isocyanate group acrylic ester is isocyanate group ethyl acrylate.
3. The pressure sensitive adhesive of claim 1, wherein the soft monomer is selected from at least one of n-butyl acrylate and isooctyl acrylate;
The hard monomer is at least one selected from styrene, vinyl acetate and methyl (meth) acrylate;
The functional monomer is at least one selected from (methyl) acrylic acid, (methyl) acrylamide and hydroxyethyl (methyl) acrylate.
4. The pressure sensitive adhesive of claim 1, wherein the tackifying resin is selected from at least one of rosin resins, petroleum resins, terpene resins, alkyl phenolic resins, and terpene phenolic resins.
5. The pressure-sensitive adhesive according to claim 1, wherein the polymerization inhibitor is at least one selected from hydroquinone and p-benzoquinone;
the cross-linking agent is a polyfunctional isocyanate curing agent;
the initiator is at least one selected from azodiisobutyronitrile and benzoyl peroxide.
6. The pressure-sensitive adhesive of claim 1, wherein the first solvent and the second solvent are independently selected from at least one of ethyl acetate, toluene, butyl acetate, acetone, and methyl ethyl ketone;
the diluent is (meth) acrylic acid.
7. A method for preparing the pressure-sensitive adhesive as claimed in any one of claims 1 to 6, comprising the steps of:
uniformly mixing polyisocyanate, an isocyanato silane coupling agent, polyester polyol and a polymerization inhibitor, then fully reacting at the temperature of 75-80 ℃, then adding isocyanato acrylate, then fully reacting at the temperature of 75-80 ℃ until the NCO content is less than 0.5%, cooling, then adding a diluent, and fully uniformly mixing to obtain organosilicon modified polyurethane acrylate;
Uniformly mixing the organosilicon modified polyurethane acrylic ester, the soft monomer, the hard monomer, the functional monomer, the initiator and the second solvent, and fully reacting at the temperature of 70-75 ℃ to obtain polyacrylate; and
And uniformly mixing the polyacrylate, the tackifying resin, the cross-linking agent and the first solvent, and defoaming to obtain the pressure-sensitive adhesive.
8. The method for producing a pressure-sensitive adhesive according to claim 7, wherein after uniformly mixing and sufficiently reacting the polyisocyanate, the isocyanatosilane coupling agent, the polyester polyol and the polymerization inhibitor, the molar ratio of hydroxyl groups to isocyanato groups is (1.8 to 2.0): 1.
9. A pressure-sensitive adhesive article comprising the pressure-sensitive adhesive of any one of claims 1 to 6.
10. The pressure-sensitive adhesive article according to claim 9, wherein the pressure-sensitive adhesive article is a pressure-sensitive adhesive tape or film.
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