CN110330901A - A kind of EVA hot-melt adhesive that adhesion strength is high - Google Patents
A kind of EVA hot-melt adhesive that adhesion strength is high Download PDFInfo
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- CN110330901A CN110330901A CN201910634147.9A CN201910634147A CN110330901A CN 110330901 A CN110330901 A CN 110330901A CN 201910634147 A CN201910634147 A CN 201910634147A CN 110330901 A CN110330901 A CN 110330901A
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- calcium carbonate
- melt adhesive
- adhesion strength
- nano
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 40
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 43
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- -1 polyethylene Polymers 0.000 claims abstract description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 9
- JZZKGJOHPIBRDB-UHFFFAOYSA-K europium(3+) prop-2-enoate Chemical compound [Eu+3].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C JZZKGJOHPIBRDB-UHFFFAOYSA-K 0.000 claims abstract description 9
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 9
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 9
- 239000004698 Polyethylene Substances 0.000 claims abstract description 7
- 239000012188 paraffin wax Substances 0.000 claims abstract description 7
- 229920000573 polyethylene Polymers 0.000 claims abstract description 7
- 239000001993 wax Substances 0.000 claims abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 159
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 83
- 239000007822 coupling agent Substances 0.000 claims description 21
- 235000006708 antioxidants Nutrition 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 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 11
- RTJGBIGSNVJSDM-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(C(C)(C)N=C=O)=C1 RTJGBIGSNVJSDM-UHFFFAOYSA-N 0.000 claims description 10
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- 239000004416 thermosoftening plastic Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- HVFZVIHIJNLIED-UHFFFAOYSA-N 2-ethenyl-1-benzofuran Chemical compound C1=CC=C2OC(C=C)=CC2=C1 HVFZVIHIJNLIED-UHFFFAOYSA-N 0.000 abstract description 8
- 230000032683 aging Effects 0.000 abstract description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 description 30
- 230000001070 adhesive effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical class C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- HBYOLNPZXLHVQA-UHFFFAOYSA-J dicalcium dicarbonate Chemical compound [Ca+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HBYOLNPZXLHVQA-UHFFFAOYSA-J 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- YDNLNVZZTACNJX-UHFFFAOYSA-N isocyanatomethylbenzene Chemical compound O=C=NCC1=CC=CC=C1 YDNLNVZZTACNJX-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of EVA hot-melt adhesive that adhesion strength is high, raw material includes: 100 parts of EVA resin, 8-19 parts of SBS thermoplastic elastomer (TPE), 4-11 parts of hydroxyl-terminated polyurethane resin, 0.2-1.3 parts of polyacrylamide, 0.15-0.8 parts of 2- vinyl -1- benzofuran, hydrogenation C by weight511-15 parts of Petropols, 5-13 parts of polyethylene wax, 1-3 parts of paraffin, 0.12-0.34 parts of antioxidant, 0.01-0.1 parts of benzoyl peroxide, 0.01-0.07 parts of europium acrylate, 13-28 parts of filler.The high EVA hot-melt adhesive of adhesion strength proposed by the present invention, adhesion strength is high, heat-resisting quantity is good, ageing-resistant performance is excellent.
Description
Technical field
The present invention relates to adhesive technology field more particularly to a kind of EVA hot-melt adhesives that adhesion strength is high.
Background technique
Hot melt adhesive be it is a kind of using thermoplastic resin as base-material and add a small amount of plasticizer, tackifier, filler, antioxidant etc.,
The adhesive being bonded using temp change, itself has many excellent properties, such as absolutely solid, solidification when
Between short, easy to operate and suitable serialization industrial production etc., at present in fields such as home decoration, unsewn binding, plastics bondings
In be widely applied.
By the difference of matrix resin, hot melt adhesive can be divided into ethylene-vinyl acetate class, styrene block elastomer class,
Polyolefins, polyamide-based, polyesters etc..Ethylene-vinyl acetate class (EVA) hot melt adhesive have excellent weatherability, it is nontoxic,
Pollution-free, the features such as preparation method is easy, be at present using a more hot melt adhesive, but its that there are adhesion strengths is not high,
The defect that heat resistance is not good enough, seriously limits its scope of application.
Summary of the invention
The invention proposes a kind of EVA hot-melt adhesives that adhesion strength is high, to solve the technical issues of proposing in background technique,
Its adhesion strength of EVA hot-melt adhesive of the present invention is high, heat-resisting quantity is good, ageing-resistant performance is excellent.
A kind of high EVA hot-melt adhesive of adhesion strength proposed by the present invention, raw material include: EVA resin 100 by weight
Part, 8-19 parts of SBS thermoplastic elastomer (TPE), 4-11 parts of hydroxyl-terminated polyurethane resin, 0.2-1.3 parts of polyacrylamide, 2- vinyl-
0.15-0.8 parts of 1- benzofuran, hydrogenation C511-15 parts of Petropols, 5-13 parts of polyethylene wax, 1-3 parts of paraffin, antioxidant
0.12-0.34 parts, 0.01-0.1 parts of benzoyl peroxide, 0.01-0.07 parts of europium acrylate, 13-28 parts of filler.
Preferably, the mass content of VA is 28-40wt% in the EVA resin.
Preferably, the SBS thermoplastic elastomer (TPE) is SBS thermoplastic elastomer (TPE) YH-792.
Preferably, the antioxidant is one of antioxidant 1010, irgasfos 168, antioxidant 264, anti-oxidant DLTP
Or a variety of mixture.
Preferably, the filler is the mixture of nano-titanium dioxide and modified nano calcium carbonate；The modified Nano carbon
Sour calcium is prepared according to following technique: being modified to obtain idol to nanometer calcium carbonate as modifying agent using Silane coupling reagent KH-570
Join agent modified nano calcium carbonate；Coupling agent modified nanometer calcium carbonate is added in DMF, methyl-prop is added after being warming up to 70-80 DEG C
Olefin(e) acid -2- hydroxyl ethyl ester and azodiisobutyronitrile are stirred to react 3-5h under the protection of nitrogen, then ultrasound 50-100min, are added
3- isopropyl-dimethyl benzyl isocyanate TMI, ultrasonic reaction 30-50min are washed, are dried to obtain the modified nano-meter caco 3
Calcium.
Preferably, the weight ratio of the modified nano calcium carbonate and nano-titanium dioxide is 5-12:2-4.
Preferably, coupling agent modified nanometer calcium carbonate, 2-hydroxyethyl methacry-late, azodiisobutyronitrile, 3- isopropyl
Base-dimethyl benzyl isocyanate TMI weight ratio is 2-3:2.5-4:0.7-1:4-6.5.
Preferably, the nanometer calcium carbonate is the mixture of Chain-shaped Nano-grade Calcium Carbonate, needle-like nano calcium carbonate, and chain is received
Rice calcium carbonate, needle-like nano calcium carbonate weight ratio be 3-9:1-2.
It is first modifying agent to nano-calcium carbonate using Silane coupling reagent KH-570 in the preparation process of modified nano calcium carbonate
Calcium is modified, and the surface that coupling agent has been introduced into nanometer calcium carbonate has been obtained coupling agent modified nanometer calcium carbonate, later with
Both coupling agent modified nanometer calcium carbonate and 2-hydroxyethyl methacry-late are raw material, using azodiisobutyronitrile as initiator, make
Reacted, introduce hydroxyl, after 3- isopropyl-dimethyl benzyl isocyanate TMI is added, the hydroxyl of introducing further with
Isocyanates is reacted, thus by Silane coupling reagent KH-570,2-hydroxyethyl methacry-late and 3- isopropyl-diformazan
Base benzyl isocyanate ester TMI has been introduced into the surface of nanometer calcium carbonate, is modified, is obtained to the surface of nanometer calcium carbonate
Modified nano calcium carbonate is added into system, is improved its dispersibility in system, is largely reduced nano-sized carbon
The agglomeration tendency of sour calcium, the double bond that surface is introduced into can react with the raw material in system, while the link that its surface introduces
Structure can be wound with EVA, improve nanometer calcium carbonate and the active force of EVA, increase its contact area with system, into one
Step enhances the mechanical property of hot melt adhesive, while having postponed the degradation of EVA macromolecular, improves the high temperature resistance of hot melt adhesive,
In addition, its surface contain with structure as polyurethanes, in addition system, improve compatible with hydroxyl-terminated polyurethane resin
Property；In preferred embodiment, the Chain-shaped Nano-grade Calcium Carbonate that has been specifically chosen special ratios, needle-like nano calcium carbonate are as nano-calcium carbonate
Calcium can play synergistic effect in addition system, and significantly improve gained hot melt adhesive coheres anti-peel property, assign gained heat
The excellent adhesive property of melten gel.
In the present invention, nanometer calcium carbonate is modified to obtain using Silane coupling reagent KH-570 as modifying agent coupling agent modified
The detailed process of nanometer calcium carbonate can be with are as follows: the mixing that ethyl alcohol and water is added in nanometer calcium carbonate, Silane coupling reagent KH-570 is molten
In liquid, wherein nanometer calcium carbonate, the weight ratio of Silane coupling reagent KH-570 are 10:1.3-2, ultrasonic 20-30min, ultrasonic power
For 200-300W, 2-5h then being stirred at 65-75 DEG C, is centrifugated at normal temperature, the revolving speed of centrifugation is 6000-8000r/
Min is dried in vacuo 3-5h at 70-80 DEG C and obtains the coupling agent modified nanometer calcium carbonate.
The high EVA hot-melt adhesive of adhesion strength of the present invention can be prepared according to following technique: by EVA resin, 2-
Vinyl -1- benzofuran, benzoyl peroxide, europium acrylate, filler are uniformly mixed with antioxidant, are added in kneading machine,
It is kneaded 5-12min at 90-100 DEG C, is then added the remaining raw materials, adjusts the temperature to 85-95 DEG C under stirring conditions, is kneaded
Material A is obtained after 45-55min；Material A is added twin-screw extrude into extrusion, the product of extrusion is obtained through cooling, granulation
The high EVA hot-melt adhesive of the adhesion strength；During the preparation process, antioxidant is preferentially added and is kneaded, avoid antioxidant
Non-uniform phenomenon is mixed, keeps the anti-aging property of gained hot melt adhesive good.
Preferably, the rate of stirring is 20-35rpm.
Adhesion strength of the present invention high EVA hot-melt adhesive in raw material, using EVA resin as major ingredient, and cooperates and is added to
SBS thermoplastic elastomer (TPE) and hydroxyl-terminated polyurethane resin, and the ratio of three is controlled, so that three is played synergistic effect, makes heat
The cohesive strength of melten gel increases, and improves the adhesion strength of gained hot melt adhesive, while improving the high temperature resistance of hot melt adhesive, together
When joined a small amount of polyacrylamide, can with water formed hydrogen bond, while in molecule contain N-H group, acid can be absorbed
Matter, the acid small molecule object that can be effectively eliminated or neutralize EVA itself a small amount of free acetic acid contained and be generated in ageing process
Matter assigns hot melt adhesive excellent vapor water barriers ability and ageing-resistant performance；2- vinyl -1- benzofuran, europium acrylate add
Enter in system, under the action of initiator benzoyl peroxide, can react with EVA, by 2- vinyl -1- benzofuran,
Europium acrylate has been introduced into EVA resin, has adjusted the content of wherein vinyl acetate, is had adjusted the polarity of system, is significantly improved
The adhesive property of hot melt adhesive, while introducing europium element, assign the preferable high temperature resistance of hot melt adhesive and ageing-resistant performance；With
The prior art is compared, and hot melt adhesive of the present invention has excellent adhesion strength, and heat-resisting quantity is good, ageing-resistant performance is excellent.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of EVA hot-melt adhesive that adhesion strength is high, raw material include: 100 parts of EVA resin, SBS thermoplastic elastomehc by weight
Property 19 parts of body, 4 parts of hydroxyl-terminated polyurethane resin, 0.9 part of polyacrylamide, 0.15 part of 2- vinyl -1- benzofuran, hydrogenation C5
15 parts of Petropols, 5 parts of polyethylene wax, 1.7 parts of paraffin, 0.15 part of antioxidant, 0.01 part of benzoyl peroxide, europium acrylate
0.07 part, 28 parts of filler.
Embodiment 2
A kind of EVA hot-melt adhesive that adhesion strength is high, raw material include: 100 parts of EVA resin, SBS thermoplastic elastomehc by weight
Property YH-7928 parts of body, 7 parts of hydroxyl-terminated polyurethane resin, 1.3 parts of polyacrylamide, 0.4 part of 2- vinyl -1- benzofuran, hydrogen
Change C511 parts of Petropols, 9 parts of polyethylene wax, 3 parts of paraffin, 0.34 part of antioxidant 1010,0.1 part of benzoyl peroxide, propylene
0.01 part of sour europium, 21 parts of filler；
Wherein, the mass content of VA is 40wt% in the EVA resin；
The filler is the mixture of nano-titanium dioxide and modified nano calcium carbonate, and modified nano calcium carbonate and nanometer
The weight ratio of titanium dioxide is 5:4；The modified nano calcium carbonate is prepared according to following technique: with silane coupling agent KH-
570 are modified nanometer calcium carbonate to obtain coupling agent modified nanometer calcium carbonate for modifying agent；By coupling agent modified nano-calcium carbonate
Calcium is added in DMF, 2-hydroxyethyl methacry-late and azodiisobutyronitrile is added after being warming up to 70 DEG C, under the protection of nitrogen
It is stirred to react 5h, then ultrasound 50min, 3- isopropyl-dimethyl benzyl isocyanate TMI is added, ultrasonic reaction 50min is washed
It washs, be dried to obtain the modified nano calcium carbonate；Wherein, coupling agent modified nanometer calcium carbonate, 2-hydroxyethyl methacry-late,
Azodiisobutyronitrile, 3- isopropyl-dimethyl benzyl isocyanate TMI weight ratio are 2:4:0.7:6.5；The nano-calcium carbonate
Calcium is the mixture of Chain-shaped Nano-grade Calcium Carbonate, needle-like nano calcium carbonate, and the weight of Chain-shaped Nano-grade Calcium Carbonate, needle-like nano calcium carbonate
Amount is than being 9:1.
Embodiment 3
A kind of EVA hot-melt adhesive that adhesion strength is high, raw material include: 100 parts of EVA resin, SBS thermoplastic elastomehc by weight
12 parts of property body YH-792,11 parts of hydroxyl-terminated polyurethane resin, 0.2 part of polyacrylamide, 2- vinyl -1- benzofuran 0.8
Part, hydrogenation C511.5 parts of Petropols, 13 parts of polyethylene wax, 1 part of paraffin, 0.2 part of irgasfos 168, anti-oxidant DLTP 0.14
Part, 0.07 part of benzoyl peroxide, 0.02 part of europium acrylate, 13 parts of filler；
Wherein, the mass content of VA is 28wt% in the EVA resin；
The filler is the mixture of nano-titanium dioxide and modified nano calcium carbonate, and modified nano calcium carbonate and nanometer
The weight ratio of titanium dioxide is 12:2；The modified nano calcium carbonate is prepared according to following technique: with silane coupling agent KH-
570 are modified nanometer calcium carbonate to obtain coupling agent modified nanometer calcium carbonate for modifying agent；By coupling agent modified nano-calcium carbonate
Calcium is added in DMF, 2-hydroxyethyl methacry-late and azodiisobutyronitrile is added after being warming up to 80 DEG C, under the protection of nitrogen
It is stirred to react 3h, then ultrasound 100min, 3- isopropyl-dimethyl benzyl isocyanate TMI is added, ultrasonic reaction 30min is washed
It washs, be dried to obtain the modified nano calcium carbonate；Wherein, coupling agent modified nanometer calcium carbonate, 2-hydroxyethyl methacry-late,
Azodiisobutyronitrile, 3- isopropyl-dimethyl benzyl isocyanate TMI weight ratio are 3:2.5:1:4；The nanometer calcium carbonate
For Chain-shaped Nano-grade Calcium Carbonate, the mixture of needle-like nano calcium carbonate, and Chain-shaped Nano-grade Calcium Carbonate, the weight of needle-like nano calcium carbonate
Than for 3:2.
Embodiment 4
A kind of EVA hot-melt adhesive that adhesion strength is high, raw material include: 100 parts of EVA resin, SBS thermoplastic elastomehc by weight
Property 12 parts of body, 8.7 parts of hydroxyl-terminated polyurethane resin, 1 part of polyacrylamide, 0.65 part of 2- vinyl -1- benzofuran, hydrogenation C5
12 parts of Petropols, 10 parts of polyethylene wax, 2.1 parts of paraffin, 0.1 part of antioxidant 1010,0.05 part of irgasfos 168, antioxidant
264 0.05 parts, 0.05 part of anti-oxidant DLTP, 0.06 part of benzoyl peroxide, 0.04 part of europium acrylate, 21 parts of filler；
Wherein, the mass content of VA is 32wt% in the EVA resin；
The SBS thermoplastic elastomer (TPE) is SBS thermoplastic elastomer (TPE) YH-792；
The filler is the mixture of nano-titanium dioxide and modified nano calcium carbonate, and modified nano calcium carbonate and nanometer
The weight ratio of titanium dioxide is 7:2；The modified nano calcium carbonate is prepared according to following technique: with silane coupling agent KH-
570 are modified nanometer calcium carbonate to obtain coupling agent modified nanometer calcium carbonate for modifying agent；By coupling agent modified nano-calcium carbonate
Calcium is added in DMF, 2-hydroxyethyl methacry-late and azodiisobutyronitrile is added after being warming up to 78 DEG C, under the protection of nitrogen
It is stirred to react 3.8h, then ultrasound 85min, 3- isopropyl-dimethyl benzyl isocyanate TMI, ultrasonic reaction 40min is added,
It washs, be dried to obtain the modified nano calcium carbonate；Wherein, coupling agent modified nanometer calcium carbonate, methacrylic acid -2- hydroxyl second
Ester, azodiisobutyronitrile, 3- isopropyl-dimethyl benzyl isocyanate TMI weight ratio are 2.7:3:0.8:5；The nanometer
Calcium carbonate is the mixture of Chain-shaped Nano-grade Calcium Carbonate, needle-like nano calcium carbonate, and Chain-shaped Nano-grade Calcium Carbonate, needle-like nano calcium carbonate
Weight ratio be 5:1.4.
Comparative example 1
With being uniquely different only in that for embodiment 4: without containing polyacrylamide in its raw material.
Comparative example 2
With being uniquely different only in that for embodiment 4: without containing 2- vinyl -1- benzofuran and acrylic acid in its raw material
Europium.
Comparative example 3
With being uniquely different only in that for embodiment 4: the modified nano calcium carbonate is prepared according to following technique: with silicon
Alkane coupling agent kh-570 is that modifying agent is modified nanometer calcium carbonate to obtain coupling agent modified nanometer calcium carbonate, i.e., the described modification
Nanometer calcium carbonate.
Hot melt adhesive in embodiment 4 and comparative example 1-3 is pressed into 160 DEG C of hot press to the glue of 1mm thickness respectively
Piece is cut into 25 × 150mm, and the film cut is placed between two pieces of aluminium flakes (25 × 200mm), in 160 DEG C of hot press
The part 50mm of two blocks of non-viscose glues of aluminium flake is all converted into right angle after cooling, with viscose glue by upper hot pressing 2min, pressure 4MPa
The part 150mm constitutes a T-type, places obtain test film for 24 hours under test conditions；According to GB/T 2791-1995 standard into
The measurement of row peel strength；Ring and ball softening point measurement is carried out according to GB/T 15332-1994 standard；
The measurement of adhesion strength: according to ASTMD1002 using universal testing machine measurement embodiment 4 and comparative example 1-3 heat
The adhesive strength of melten gel.At room temperature, substrate sizes are 150mm × 30mm × 2mm, and gluing length is about 3cm.
As a result as shown in the table:
The hot melt adhesive of embodiment 4 and comparative example 4, aging 30 days at 80 DEG C, adhesive property is basically unchanged, and is compared
The hot melt adhesive of example 2 and comparative example 3,30 days its adhesive properties of aging are declined at 70 DEG C.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of EVA hot-melt adhesive that adhesion strength is high, which is characterized in that its raw material include: by weight 100 parts of EVA resin,
8-19 parts of SBS thermoplastic elastomer (TPE), 4-11 parts of hydroxyl-terminated polyurethane resin, 0.2-1.3 parts of polyacrylamide, 2- vinyl -1-
0.15-0.8 parts of benzofuran, hydrogenation C511-15 parts of Petropols, 5-13 parts of polyethylene wax, 1-3 parts of paraffin, antioxidant 0.12-
0.34 part, 0.01-0.1 parts of benzoyl peroxide, 0.01-0.07 parts of europium acrylate, 13-28 parts of filler.
2. the high EVA hot-melt adhesive of adhesion strength according to claim 1, which is characterized in that the quality of VA in the EVA resin
Content is 28-40wt%.
3. the high EVA hot-melt adhesive of adhesion strength according to claim 1 or claim 2, which is characterized in that the SBS thermoplastic elastic
Body is SBS thermoplastic elastomer (TPE) YH-792.
4. the high EVA hot-melt adhesive of adhesion strength according to claim 1 or claim 2, which is characterized in that the antioxidant is antioxidant
1010, the mixture of one or more of irgasfos 168, antioxidant 264, anti-oxidant DLTP.
5. the high EVA hot-melt adhesive of adhesion strength according to claim 1 or claim 2, which is characterized in that the filler is nano-silica
Change the mixture of titanium and modified nano calcium carbonate；The modified nano calcium carbonate is prepared according to following technique: with silane idol
Connection agent KH-570 is that modifying agent is modified nanometer calcium carbonate to obtain coupling agent modified nanometer calcium carbonate；It is received coupling agent modified
Rice calcium carbonate is added in DMF, 2-hydroxyethyl methacry-late and azodiisobutyronitrile is added after being warming up to 70-80 DEG C, in nitrogen
Protection under be stirred to react 3-5h, 3- isopropyl-dimethyl benzyl isocyanate TMI is added in then ultrasound 50-100min, surpasses
Phonoresponse 30-50min is washed, is dried to obtain the modified nano calcium carbonate.
6. the high EVA hot-melt adhesive of adhesion strength according to claim 5, which is characterized in that the modified nano calcium carbonate with
The weight ratio of nano-titanium dioxide is 5-12:2-4.
7. according to the high EVA hot-melt adhesive of the adhesion strength of claim 5 or 6, which is characterized in that coupling agent modified nano-calcium carbonate
Calcium, 2-hydroxyethyl methacry-late, azodiisobutyronitrile, 3- isopropyl-dimethyl benzyl isocyanate TMI weight ratio are
2-3:2.5-4:0.7-1:4-6.5.
8. according to the high EVA hot-melt adhesive of the adhesion strength of claim 5 or 6, which is characterized in that the nanometer calcium carbonate is chain
The mixture of shape nanometer calcium carbonate, needle-like nano calcium carbonate, and Chain-shaped Nano-grade Calcium Carbonate, the weight ratio of needle-like nano calcium carbonate are
3-9:1-2.
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| CN113403003A (en) * | 2021-06-23 | 2021-09-17 | 泉州中宝鞋材有限公司 | Formula and preparation method of high-hardness hot-melt adhesive sheet |
| CN113913131A (en) * | 2021-11-05 | 2022-01-11 | 龚郁蓉 | Modified EVA hot melt adhesive and preparation method thereof |
| CN114262582A (en) * | 2022-01-21 | 2022-04-01 | 广东汇齐新材料有限公司 | High-temperature-resistant EVA hot-melt adhesive film and preparation process thereof |
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| CN115044348A (en) * | 2022-07-13 | 2022-09-13 | 广州市嘉雁粘合剂有限公司 | EMS label hot melt adhesive with strong peeling force and easy slitting and preparation method thereof |
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