CN116694127B - High-adhesion heating painting ink and preparation process thereof - Google Patents
High-adhesion heating painting ink and preparation process thereof Download PDFInfo
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- CN116694127B CN116694127B CN202310775631.XA CN202310775631A CN116694127B CN 116694127 B CN116694127 B CN 116694127B CN 202310775631 A CN202310775631 A CN 202310775631A CN 116694127 B CN116694127 B CN 116694127B
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- 238000010438 heat treatment Methods 0.000 title claims abstract description 54
- 238000010422 painting Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000006229 carbon black Substances 0.000 claims abstract description 70
- -1 polypropylene Polymers 0.000 claims abstract description 67
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 58
- 239000004743 Polypropylene Substances 0.000 claims abstract description 57
- 229920001155 polypropylene Polymers 0.000 claims abstract description 57
- 239000000945 filler Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000001721 carbon Chemical class 0.000 claims abstract description 26
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 24
- 125000003396 thiol group Chemical class [H]S* 0.000 claims abstract description 21
- 229920001577 copolymer Polymers 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 150000003505 terpenes Chemical class 0.000 claims abstract description 14
- 235000007586 terpenes Nutrition 0.000 claims abstract description 14
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims abstract description 13
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 13
- 230000001070 adhesive effect Effects 0.000 claims abstract description 13
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 13
- 239000000853 adhesive Substances 0.000 claims abstract description 12
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims abstract description 12
- 229920002635 polyurethane Polymers 0.000 claims abstract description 11
- 239000004814 polyurethane Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 239000002562 thickening agent Substances 0.000 claims description 15
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 14
- 229940047670 sodium acrylate Drugs 0.000 claims description 14
- 150000001263 acyl chlorides Chemical class 0.000 claims description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 11
- 229920001568 phenolic resin Polymers 0.000 claims description 11
- 239000005011 phenolic resin Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- 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 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000000976 ink Substances 0.000 description 48
- 229920005749 polyurethane resin Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000007639 printing Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 239000000758 substrate Substances 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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to the technical field of ink, in particular to high-adhesion heating painting ink and a preparation process thereof. The method specifically comprises the following steps: s1: sequentially oxidizing and acyl-chlorinating carbon black, and then reacting with hydroxyl-terminated polybutadiene acrylonitrile to obtain modified carbon black; s2: mixing nano alumina and nano titanium dioxide, and modifying by using a silane coupling agent to obtain modified filler; s3: grafting terpene resin and butadiene rubber on chlorinated polypropylene to obtain modified polypropylene resin; s4: and uniformly mixing the modified carbon black, the modified filler, the modified polypropylene resin, the mercapto graphene, the polyurethane, the styrene-acrylic ester copolymer, the auxiliary agent, the solvent and the deionized water to obtain the heating painting ink with high adhesive force.
Description
Technical Field
The invention relates to the technical field of ink, in particular to high-adhesion heating painting ink and a preparation process thereof.
Background
The ink is used for forming graphic information in the printing process, and the paste adhesive with certain fluidity is uniformly mixed, so that patterns and characters can be clearly represented by printing or spray-painting the paste adhesive on a printing stock.
As social demands increase, so too does the variety of inks. In the heating picture, the existing printing ink is generally poor in thermal stability, so that the ink is easy to fall off and crack when heated, and poor in adhesive force, so that time and resources are wasted.
Therefore, the invention provides the heating painting ink with high adhesive force.
Disclosure of Invention
The invention aims to provide a high-adhesion heating painting ink and a preparation process thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
A high adhesion heat-generating painting ink comprising the following components: the weight portions are as follows: 5-10 parts of modified carbon black, 6-10 parts of modified filler, 10-18 parts of modified polypropylene resin, 6-12 parts of mercapto graphene, 5-10 parts of polyurethane, 10-15 parts of styrene-acrylate copolymer, 30-50 parts of solvent, 10-20 parts of deionized water, 1-1.5 parts of dispersing agent and 0.5-1 part of thickener.
Further, the preparation steps of the high-adhesion heating painting ink are as follows:
S1: sequentially oxidizing and acyl-chlorinating carbon black, and then reacting with hydroxyl-terminated polybutadiene acrylonitrile to obtain modified carbon black;
Further, the preparation method of the modified carbon black comprises the following steps:
(1) Adding carbon black into a strong oxidant solution with the concentration of 1-5 mol/L, carrying out reflux oxidation for 12-24 hours at the temperature of 90-110 ℃, naturally cooling to room temperature, and washing to obtain oxidized carbon black;
(2) Adding oxidized carbon black into 2-5 mol/L thionyl chloride solution, reacting for 6-12 h under the water bath condition of 50-70 ℃, naturally cooling to room temperature, and removing thionyl chloride by suction filtration to obtain acyl chloride carbon black;
(3) Adding acyl chloride carbon black and hydroxyl-terminated polybutadiene acrylonitrile into petroleum ether, mechanically stirring under the water bath condition of 30-50 ℃, carrying out reflux reaction for 24-48 h, naturally cooling to room temperature, filtering, and drying to obtain the modified carbon black.
Further, the particle size of the carbon black is 1 to 40nm.
Further, the strong oxidizing agent includes, but is not limited to, any one of a nitric acid solution, a hydrogen peroxide solution, a perchloric acid solution, and a potassium permanganate solution.
Further, the mass ratio of the acyl chloride carbon black, the hydroxyl-terminated polybutadiene acrylonitrile and the petroleum ether is (1-3): 1 (2-5).
The raw carbon black has poor compatibility with other resin materials in the ink, so that the adhesive force performance of the ink is poor; the method comprises the steps of adding a strong oxidant to increase the carboxyl content on the surface of the carbon black, improving the surface activity of the carbon black, increasing the grafting rate, carrying out chloracylation on carboxyl under the action of thionyl chloride, reacting with hydroxyl-terminated polybutadiene acrylonitrile, and finally introducing a polybutadiene acrylonitrile chain end on the surface of the carbon black. On the one hand, the hydroxyl-terminated polybutadiene acrylonitrile can be used as an adhesive, so that the adhesive property can be improved to a certain extent, and in addition, the end of the polybutene acrylonitrile chain can promote the compatibility with the resin added in the invention, so that the adhesive capability of the ink is improved.
S2: mixing nano alumina and nano titanium dioxide, and modifying by using a silane coupling agent to obtain modified filler;
Further, the preparation method of the modified filler comprises the following steps: adding nano titanium dioxide and nano aluminum oxide into a mixer according to a certain proportion, heating to 70-90 ℃, stirring at a rotating speed of 50-100 r/min, adding a certain mass of silane coupling agent into the mixer in a spraying manner, preserving heat for 3-6 h, and naturally cooling to room temperature to obtain the modified filler.
Further, the mixing ratio of the nano titanium dioxide to the nano aluminum oxide is 2 (1-2).
Further, the silane coupling agent is a mercapto group-containing silane coupling agent, including but not limited to any one of KBM802, KBM803, and KBE 803.
Further, the addition amount of the silane coupling agent is 1-5% of the total mass of the nano titanium dioxide and the nano aluminum oxide.
The nano titanium dioxide and the nano aluminum oxide are mixed according to a proportion, and then modified by using a silane coupling agent with sulfhydryl groups. On the one hand, in order to ensure that the ink has good ultraviolet resistance and is not easy to age, a certain amount of titanium dioxide is added, and in addition, a certain amount of aluminum oxide is added into the filler in consideration of the adhesion problem of the ink on the composite board made of aluminum and polypropylene. The silane coupling agent has mercapto, which can perform click reaction with unsaturated double bond in resin, raise the compatibility of stuffing and resin, inhibit oxidation and promote the oxidation resistance of ink.
S3: grafting terpene resin and butadiene rubber on chlorinated polypropylene to obtain modified polypropylene resin;
further, the preparation method of the modified polypropylene resin comprises the following steps:
(1) Adding chlorinated polypropylene into toluene, heating to 50-70 ℃, and stirring to dissolve the chlorinated polypropylene to obtain a resin solution;
(2) Heating the resin solution to 90-110 ℃, adding terpene phenolic resin, butadiene rubber and an initiator, stirring and reacting for 5-10 h, cooling to room temperature, and filtering to obtain the modified polypropylene resin.
Further, the mass of the toluene is 3-8 times of that of the chlorinated polypropylene.
Further, the mass ratio of the chlorinated polypropylene to the terpene phenolic resin to the butadiene rubber is 1 (0.1-0.5) to 0-0.3.
Further, the initiator includes, but is not limited to, one or more combinations of benzoyl peroxide, cyclohexane peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, and t-butyl hydroperoxide.
Further, the addition amount of the initiator is 1-5% of the mass of the chlorinated polypropylene.
In the method, the butadiene rubber is grafted on the chlorinated polypropylene, so that the heat resistance and ageing resistance of the chlorinated polypropylene are regulated, in addition, the terpene phenolic resin is grafted, the content of benzene ring structures in the resin is increased, the thermal stability of the resin is further improved, and the thermal stability of the whole ink is improved.
S4: and uniformly mixing the modified carbon black, the modified filler, the modified polypropylene resin, the mercapto graphene, the polyurethane, the styrene-acrylic ester copolymer, the auxiliary agent, the solvent and the deionized water to obtain the heating painting ink with high adhesive force.
Further, the preparation method of the high-adhesion heating painting ink comprises the following steps:
(1) Mixing and stirring the modified polypropylene resin, polyurethane, styrene-acrylic ester copolymer, an auxiliary agent, a solvent and deionized water for 10-20 min, heating to 70-90 ℃ in a water bath, and continuously stirring for 1-2 h to obtain a mixed resin;
(2) And cooling the mixed resin to 50-70 ℃, adding the modified carbon black, the modified filler and the mercapto graphene into the mixed resin, and stirring at a rotating speed of 500-800 r/min for 30-60 min to obtain the high-adhesion heating painting ink.
Further, the auxiliary agent is a dispersing agent and a thickening agent.
Further, the dispersant includes, but is not limited to, a combination of one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, and sodium acrylate.
Further, the solvent includes, but is not limited to, a combination of one or more of DMF, cyclohexane, isopropanol, and tetrahydrofuran.
The polyurethane is added into the resin, wherein isocyanate groups in the polyurethane can react with phenolic hydroxyl groups in the modified polypropylene resin to form a stable structure, and the resin can be well compatible with styrene-acrylic ester copolymer and solvent, so that the resin compatibility is ensured, and the adhesion performance of the ink on a substrate is greatly ensured; the graphene selects mercapto graphene, and the mercapto group of the mercapto graphene and the mercapto group in the silane coupling agent react with unsaturated bonds in the polymer together, so that the compatibility of the mercapto graphene in the polymer is promoted to a certain extent; meanwhile, polyurethane and modified polypropylene resin are combined, and the thermal stability of the printing ink can be further ensured by the cooperation of the filler and the graphene, so that the heat resistance of the printing ink is ensured, and the ageing is not easy to occur
Compared with the prior art, the invention has the following beneficial effects: according to the invention, the polybutadiene acrylonitrile chain end is introduced on the surface of the carbon black, so that the compatibility of the carbon black and resin is promoted; in the selection of the filler, the combination of nano alumina and nano titanium dioxide is selected, so that the ageing resistance of the ink is improved, and the compatibility is promoted; the silane coupling agent with mercapto is used in the modification of the filler, and reacts with the unsaturated double bond in the resin together with the mercapto graphene, so that the molecular acting force in the polymer is stronger, and the compatibility of the filler and the polymer is ensured; in order to ensure compatibility and improve the thermal stability of the resin to a certain extent, the invention grafts the terpene phenolic resin and the butadiene rubber on the chlorinated polypropylene, wherein the phenolic hydroxyl group in the terpene phenolic resin can be combined with the isocyanate group in the polyurethane, and the compatibility of the polymer can be promoted. The compatibility of all components in the raw materials is guaranteed, so that the ink can show better adhesion performance and thermal stability; and the raw materials are selected, the structure of the raw materials is similar to that of the base material, the adhesion performance of the raw materials and the base material can be further improved, and the high-adhesion ink for the heating picture is comprehensively obtained.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, the purity of carbon black was 99.9%, the particle size was 1 to 40nm (New Material technology Co., ltd.) and the purity of hydrogen peroxide was 96% (Mao Ming Seisakusho chemical Co., ltd.) and the purity of thionyl chloride was 99%, CAS number: 7719-09-7 (Prhua chemical Co., ltd., changzhou) petroleum ether purity 99.9% (Jinan chemical Co., ltd.), hydroxyl-terminated polybutadiene acrylonitrile purity 99%, product number: HTBN (Wuhan Rong and Brilliant Biotechnology Co., ltd.), nano alumina with a purity of 99%, a particle size of 3-10 nm (Yuan mu Bo New Material Co., ltd.), nano titanium dioxide with a purity of 99.8%, a particle size of 5-10 nm (KBM Co., ltd.), KBM803 with a purity of 95% (Shanghai Yuan leaf Biotechnology Co., ltd.), chlorinated polypropylene with a purity of 99% (Hubei Fangde New Material Co., ltd.), toluene with a purity of 99% (Jiangyin Euro chemical Co., ltd.), terpene phenolic resin with a purity of 99%, model: 803L, CAS number: 68648-57-7 (Shanghai Dong tiger Co., ltd.) butadiene rubber BR9000 purity 98%, CAS number: 9003-17-2 (Long Kangcheng Fine chemical Co., ltd. In Hubei), benzoyl peroxide with a purity of 75% (Jinan Toyo chemical Co., ltd., water-borne polyurethane resin with a purity of 95%, CAS number: 51852-81-4, cat No.: 008B (Zigbao Wei New Material science Co., ltd.) the purity of the styrene-acrylate copolymer was 99%, model: TH 8163 (Xiamen Kang Dilong trade company, inc.) purity of sodium acrylate 98%, CAS number: 7446-81-3 (Henan Witaziki chemical Co., ltd.) has a DMF purity of 99% (West An Jinyuan Biotechnology Co., ltd.).
Example 1: a preparation process of high-adhesion heating painting ink comprises the following steps:
S1: (1) Adding 11 parts of carbon black into 3mol/L hydrogen peroxide solution, carrying out reflux oxidation for 15 hours at 100 ℃, naturally cooling to room temperature, and washing to obtain 10.90 parts of oxidized carbon black;
(2) Adding 10 parts of oxidized carbon black into 3mol/L thionyl chloride solution, reacting for 8 hours under the water bath condition of 60 ℃, naturally cooling to room temperature, and removing thionyl chloride by suction filtration to obtain 10.3 parts of acyl chloride carbon black;
(3) 10 parts of acyl chloride carbon black and 5 parts of hydroxyl-terminated polybutadiene acrylonitrile are added into 20 parts of petroleum ether, under the water bath condition of 35 ℃, the mixture is mechanically stirred and subjected to reflux reaction for 24 hours, and after the mixture is naturally cooled to room temperature, the modified carbon black is obtained through filtration and drying.
S2: adding 8 parts of nano titanium dioxide and 8 parts of nano aluminum oxide into a mixer, heating to 80 ℃, stirring at a rotating speed of 60r/min, simultaneously adding 0.4 part of KBM803 into the mixer in a spraying manner, preserving heat for 4 hours, and naturally cooling to room temperature to obtain the modified filler.
S3: 15 parts of chlorinated polypropylene is added into 50 parts of toluene, heated to 60 ℃, and stirred to dissolve the chlorinated polypropylene; heating to 100 ℃, adding 3 parts of terpene phenolic resin, 1 part of butadiene rubber and 0.2 part of benzoyl peroxide, stirring and reacting for 6 hours, cooling to room temperature, and filtering to obtain the modified polypropylene resin.
S4: (1) Mixing and stirring modified polypropylene resin, aqueous polyurethane resin, styrene-acrylic ester copolymer, sodium acrylate, thickener, isopropanol and deionized water for 15min, heating to 80 ℃ in water bath, and continuously stirring for 1h to obtain mixed resin;
(2) And cooling the mixed resin to 50 ℃, adding the modified carbon black, the modified filler and the mercapto graphene into the mixed resin, and stirring at 600r/min for 30min to obtain the high-adhesion heating painting ink.
The high-adhesion heating painting ink comprises the following components: the weight portions are as follows: 8 parts of modified carbon black, 8 parts of modified filler, 13 parts of modified polypropylene resin, 7 parts of sulfhydryl graphene, 7 parts of waterborne polyurethane resin, 15 parts of styrene-acrylate copolymer, 40 parts of isopropanol, 15 parts of deionized water, 1.5 parts of sodium acrylate and 0.7 part of thickener.
Example 2: a preparation process of high-adhesion heating painting ink comprises the following steps:
s1: (1) Adding 11 parts of carbon black into a 1mol/L hydrogen peroxide solution, carrying out reflux oxidation for 15 hours at 100 ℃, naturally cooling to room temperature, and washing to obtain 10.91 parts of oxidized carbon black;
(2) Adding 10 parts of oxidized carbon black into 2mol/L thionyl chloride solution, reacting for 8 hours under the water bath condition of 60 ℃, naturally cooling to room temperature, and removing thionyl chloride by suction filtration to obtain 10.3 parts of acyl chloride carbon black;
(3) 10 parts of acyl chloride carbon black and 10 parts of hydroxyl-terminated polybutadiene acrylonitrile are added into 20 parts of petroleum ether, under the water bath condition of 35 ℃, the mixture is mechanically stirred and subjected to reflux reaction for 24 hours, and after the mixture is naturally cooled to room temperature, the modified carbon black is obtained through filtration and drying.
S2: adding 8 parts of nano titanium dioxide and 8 parts of nano aluminum oxide into a mixer, heating to 80 ℃, stirring at a rotating speed of 60r/min, simultaneously adding 0.16 part of KBM803 into the mixer in a spraying manner, preserving heat for 4 hours, and naturally cooling to room temperature to obtain the modified filler.
S3: 15 parts of chlorinated polypropylene is added into 50 parts of toluene, heated to 50 ℃, and stirred to dissolve the chlorinated polypropylene; heating to 90 ℃, adding 3 parts of terpene phenolic resin, 1 part of butadiene rubber and 0.2 part of benzoyl peroxide, stirring and reacting for 6 hours, cooling to room temperature, and filtering to obtain the modified polypropylene resin.
S4: (1) Mixing and stirring modified polypropylene resin, aqueous polyurethane resin, styrene-acrylic ester copolymer, sodium acrylate, thickener, isopropanol and deionized water for 10min, heating to 70 ℃ in water bath, and continuously stirring for 1h to obtain mixed resin;
(2) And cooling the mixed resin to 50 ℃, adding the modified carbon black, the modified filler and the mercapto graphene into the mixed resin, and stirring at a rotating speed of 500r/min for 30min to obtain the high-adhesion heating painting ink.
The high-adhesion heating painting ink comprises the following components: the weight portions are as follows: 8 parts of modified carbon black, 8 parts of modified filler, 13 parts of modified polypropylene resin, 7 parts of sulfhydryl graphene, 7 parts of waterborne polyurethane resin, 15 parts of styrene-acrylate copolymer, 40 parts of isopropanol, 15 parts of deionized water, 1.5 parts of sodium acrylate and 0.7 part of thickener.
Example 3: a preparation process of high-adhesion heating painting ink comprises the following steps:
s1: (1) Adding 11 parts of carbon black into 5mol/L hydrogen peroxide solution, carrying out reflux oxidation for 15 hours at 100 ℃, naturally cooling to room temperature, and washing to obtain 10.86 parts of oxidized carbon black;
(2) Adding 10 parts of oxidized carbon black into 5mol/L thionyl chloride solution, reacting for 8 hours under the water bath condition of 60 ℃, naturally cooling to room temperature, and removing thionyl chloride by suction filtration to obtain 10.4 parts of acyl chloride carbon black;
(3) 10 parts of acyl chloride carbon black and 3.5 parts of hydroxyl-terminated polybutadiene acrylonitrile are added into 16.6 parts of petroleum ether, the mixture is mechanically stirred under the water bath condition of 35 ℃ and subjected to reflux reaction for 24 hours, and the mixture is naturally cooled to room temperature, filtered and dried to obtain the modified carbon black.
S2: adding 8 parts of nano titanium dioxide and 8 parts of nano aluminum oxide into a mixer, heating to 80 ℃, stirring at a rotating speed of 60r/min, simultaneously adding 0.5 part of KBM803 into the mixer in a spraying manner, preserving heat for 4 hours, and naturally cooling to room temperature to obtain the modified filler.
S3: 15 parts of chlorinated polypropylene is added into 50 parts of toluene, heated to 70 ℃, and stirred to dissolve the chlorinated polypropylene; heating to 110 ℃, adding 3 parts of terpene phenolic resin, 1 part of butadiene rubber and 0.2 part of benzoyl peroxide, stirring and reacting for 10 hours, cooling to room temperature, and filtering to obtain the modified polypropylene resin.
S4: (1) Mixing and stirring modified polypropylene resin, aqueous polyurethane resin, styrene-acrylic ester copolymer, sodium acrylate, thickener, isopropanol and deionized water for 20min, heating to 90 ℃ in water bath, and continuously stirring for 2h to obtain mixed resin;
(2) And cooling the mixed resin to 70 ℃, adding the modified carbon black, the modified filler and the mercapto graphene into the mixed resin, and stirring at the rotating speed of 800r/min for 60min to obtain the high-adhesion heating painting ink.
The high-adhesion heating painting ink comprises the following components: the weight portions are as follows: 8 parts of modified carbon black, 8 parts of modified filler, 13 parts of modified polypropylene resin, 7 parts of sulfhydryl graphene, 7 parts of waterborne polyurethane resin, 15 parts of styrene-acrylate copolymer, 40 parts of isopropanol, 15 parts of deionized water, 1.5 parts of sodium acrylate and 0.7 part of thickener.
Comparative example 1: the high-adhesion heating painting ink comprises the following components: the weight portions are as follows: 5 parts of modified carbon black, 6 parts of modified filler, 10 parts of modified polypropylene resin, 7 parts of sulfhydryl graphene, 7 parts of waterborne polyurethane resin, 15 parts of styrene-acrylic ester copolymer, 40 parts of isopropanol, 15 parts of deionized water, 1.5 parts of sodium acrylate, 0.7 part of thickener and the like in example 1;
Comparative example 2: the high-adhesion heating painting ink comprises the following components: the weight portions are as follows: 10 parts of modified carbon black, 10 parts of modified filler, 18 parts of modified polypropylene resin, 7 parts of sulfhydryl graphene, 7 parts of waterborne polyurethane resin, 15 parts of styrene-acrylic ester copolymer, 40 parts of isopropanol, 15 parts of deionized water, 1.5 parts of sodium acrylate, 0.7 part of thickener and the like in example 1;
Comparative example 3: the carbon black is not modified, and the high-adhesion heating painting ink comprises the following components: the weight portions are as follows: 8 parts of carbon black, 8 parts of modified filler, 13 parts of modified polypropylene resin, 7 parts of sulfhydryl graphene, 7 parts of waterborne polyurethane resin, 15 parts of styrene-acrylic ester copolymer, 40 parts of isopropanol, 15 parts of deionized water, 1.5 parts of sodium acrylate, 0.7 part of thickener and the like in example 1;
comparative example 4: the chlorinated polypropylene is not modified, and the high-adhesion heating painting ink comprises the following components: the weight portions are as follows: 8 parts of modified carbon black, 8 parts of modified filler, 13 parts of chlorinated polypropylene, 7 parts of sulfhydryl graphene, 7 parts of waterborne polyurethane resin, 15 parts of styrene-acrylate copolymer, 40 parts of isopropanol, 15 parts of deionized water, 1.5 parts of sodium acrylate and 0.7 part of thickener.
Comparative example 5: the filler is only titanium dioxide, and is modified by vinyl triethoxysilane: otherwise, the same as in example 1;
S2: and (3) adding 16 parts of nano titanium dioxide into a mixer, heating to 80 ℃, stirring at a rotating speed of 60r/min, simultaneously adding 0.4 part of vinyl triethoxysilane into the mixer in a spraying manner, preserving heat for 4 hours, and naturally cooling to room temperature to obtain the modified titanium dioxide.
Comparative example 6: the carbon black and the chlorinated polypropylene are not modified, and the filler is only titanium dioxide and is modified by vinyl triethoxysilane; the high-adhesion heating painting ink comprises the following components: the weight portions are as follows: 8 parts of carbon black, 8 parts of modified titanium dioxide, 13 parts of chlorinated polypropylene, 7 parts of sulfhydryl graphene, 7 parts of waterborne polyurethane resin, 15 parts of styrene-acrylate copolymer, 40 parts of isopropanol, 15 parts of deionized water, 1.5 parts of sodium acrylate and 0.7 part of thickener.
Performance test: the adhesive force test is carried out on the heating painting inks with high adhesive force prepared in examples 1-3 and comparative examples 1-6 by adopting a viscous pull method at different temperatures, each ink is respectively coated and printed on an aluminum-plastic composite board, then an adhesive tape is stuck on the printing ink surface, the adhesive tape is rolled for 3 times in one direction by using a compression roller with constant load, and after the adhesive tape is placed for 10min, a sample with the length of 20cm and the width of 1.5cm is prepared according to a T-type peel strength test method, and the T-type peel strength of the sample is tested by using a peel tester.
From the test data in the table above, it can be seen that: the high-adhesion heating painting ink has excellent adhesion fastness, and the comparative examples and comparative examples have obvious influence on the adhesion capability of the ink on carbon black modification, filler selection, coupling agent selection and chlorinated polypropylene modification, and also have obvious influence on the thermal stability of the ink, so that the adhesion capability of the ink at different temperatures is influenced.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A preparation process of high-adhesion heating painting ink is characterized by comprising the following steps of: the method comprises the following steps:
S1: sequentially oxidizing and acyl-chlorinating carbon black, and then reacting with hydroxyl-terminated polybutadiene acrylonitrile to obtain modified carbon black;
The preparation method of the modified carbon black comprises the following steps: (1) Adding carbon black into a strong oxidant solution with the concentration of 1-5 mol/L, carrying out reflux oxidation for 12-24 hours at the temperature of 90-110 ℃, naturally cooling to room temperature, and washing to obtain oxidized carbon black; (2) Adding oxidized carbon black into a 2-5 mol/L thionyl chloride solution, reacting for 6-12 hours under the water bath condition of 50-70 ℃, naturally cooling to room temperature, and removing thionyl chloride by suction filtration to obtain acyl chloride carbon black; (3) Adding acyl chloride carbon black and hydroxyl-terminated polybutadiene acrylonitrile into petroleum ether, mechanically stirring under the water bath condition of 30-50 ℃, carrying out reflux reaction for 24-48 h, naturally cooling to room temperature, filtering, and drying to obtain modified carbon black; wherein the granularity of the carbon black is 1-40 nm; the strong oxidant comprises any one of nitric acid solution, hydrogen peroxide solution, perchloric acid solution and potassium permanganate solution; the mass ratio of the acyl chloride carbon black to the hydroxyl-terminated polybutadiene acrylonitrile to the petroleum ether is (1-3) 1 (2-5);
S2: mixing nano alumina and nano titanium dioxide, and modifying by using a silane coupling agent to obtain modified filler;
The preparation method of the modified filler comprises the following steps: uniformly mixing nano titanium dioxide and nano aluminum oxide at the rotation speed of 50-100 r/min at the temperature of 70-90 ℃, simultaneously adding a silane coupling agent into the mixture in a spraying manner, preserving heat for 3-6 hours, and naturally cooling the mixture to room temperature to obtain modified filler; wherein, the mixing proportion of the nano titanium dioxide and the nano aluminum oxide is 2 (1-2); the silane coupling agent is a mercapto-containing silane coupling agent and comprises any one of KBM802, KBM803 and KBE 803; the addition amount of the silane coupling agent is 1-5% of the total mass of the nano titanium dioxide and the nano aluminum oxide;
s3: grafting terpene resin and butadiene rubber on chlorinated polypropylene to obtain modified polypropylene resin;
The preparation method of the modified polypropylene resin comprises the following steps: adding chlorinated polypropylene into toluene, heating to 50-70 ℃, stirring to dissolve the chlorinated polypropylene, heating to 90-110 ℃, adding terpene phenolic resin, butadiene rubber and an initiator, stirring to react for 5-10 hours, cooling to room temperature, and filtering to obtain modified polypropylene resin; wherein the mass of toluene is 3-8 times of that of chlorinated polypropylene; the mass ratio of the chlorinated polypropylene to the terpene phenolic resin to the butadiene rubber is 1 (0.1-0.5): 0-0.3); the initiator comprises one or more of benzoyl peroxide, cyclohexane peroxide, methyl ethyl ketone peroxide, dicumyl peroxide and tert-butyl hydroperoxide; the addition amount of the initiator is 1-5% of the mass of the chlorinated polypropylene;
S4: and uniformly mixing the modified carbon black, the modified filler, the modified polypropylene resin, the mercapto graphene, the polyurethane, the styrene-acrylic ester copolymer, the auxiliary agent, the solvent and the deionized water to obtain the heating painting ink with high adhesive force.
2. The process for preparing the high-adhesion heating picture ink according to claim 1, which is characterized in that: s4, the preparation method of the high-adhesion heating painting ink comprises the following steps: mixing and stirring the modified polypropylene resin, polyurethane, a styrene-acrylic ester copolymer, an auxiliary agent, a solvent and deionized water for 10-20 min, heating to 70-90 ℃ in a water bath, and continuously stirring for 1-2 h; and cooling to 50-70 ℃, adding the modified carbon black, the modified filler and the mercapto graphene into the mixed resin, and stirring at a rotating speed of 500-800 r/min for 30-60 min to obtain the high-adhesion heating painting ink.
3. The process for preparing the high-adhesion heating picture ink according to claim 2, which is characterized in that: the auxiliary agent is a dispersing agent and a thickening agent; the dispersing agent comprises one or a combination of more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium acrylate; the solvent comprises one or more of DMF, cyclohexane, isopropanol and tetrahydrofuran.
4. The process for preparing the high-adhesion heating painting ink according to any one of claims 1 to 3, which is characterized in that: the high-adhesion heating painting ink comprises the following components: the weight portions are as follows: 5-10 parts of modified carbon black, 6-10 parts of modified filler, 10-18 parts of modified polypropylene resin, 6-12 parts of mercapto graphene, 5-10 parts of polyurethane, 10-15 parts of styrene-acrylate copolymer, 30-50 parts of solvent, 10-20 parts of deionized water and 1.5-2.5 parts of auxiliary agent; wherein the auxiliary agent comprises 1-1.5 parts of dispersing agent and 0.5-1 part of thickening agent.
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| WO2023114574A1 (en) * | 2021-12-14 | 2023-06-22 | Dupont Electronics, Inc. | Inkjet ink and primer fluid set |
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| US5316885A (en) * | 1990-08-14 | 1994-05-31 | Kao Corporation | Pulverulent ink and printing methods |
| JP2007112884A (en) * | 2005-10-19 | 2007-05-10 | Fujifilm Corp | Composition, ink for forming colored film for display device, light shielding film for display device, light shielding material, substrate with light shielding film, color filter, liquid crystal display element and liquid crystal display device |
| CN102746472A (en) * | 2012-04-20 | 2012-10-24 | 苏州兴业材料科技股份有限公司 | Modified polypropylene special resin and preparation method thereof |
| WO2022120565A1 (en) * | 2020-12-08 | 2022-06-16 | 苏州烯时代材料科技有限公司 | Graphene heating ink, preparation method therefor, and application thereof |
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