CN111732853B - Thermal foaming ink with excellent adhesion and preparation method and application thereof - Google Patents
Thermal foaming ink with excellent adhesion and preparation method and application thereof Download PDFInfo
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- CN111732853B CN111732853B CN201910229145.1A CN201910229145A CN111732853B CN 111732853 B CN111732853 B CN 111732853B CN 201910229145 A CN201910229145 A CN 201910229145A CN 111732853 B CN111732853 B CN 111732853B
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- 238000005187 foaming Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 239000000049 pigment Substances 0.000 claims abstract description 19
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 18
- 229920006378 biaxially oriented polypropylene Polymers 0.000 claims abstract description 8
- 239000011127 biaxially oriented polypropylene Substances 0.000 claims abstract description 8
- 229920005792 styrene-acrylic resin Polymers 0.000 claims abstract description 8
- 229920000728 polyester Polymers 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 23
- -1 polysiloxane Polymers 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 18
- 239000000975 dye Substances 0.000 claims description 18
- 229930195729 fatty acid Natural products 0.000 claims description 18
- 239000000194 fatty acid Substances 0.000 claims description 18
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000004925 Acrylic resin Substances 0.000 claims description 16
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000002318 adhesion promoter Substances 0.000 claims description 14
- 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 13
- 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 13
- 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 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 150000002191 fatty alcohols Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 239000004359 castor oil Substances 0.000 claims description 5
- 235000019438 castor oil Nutrition 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 5
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical group OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- 230000020477 pH reduction Effects 0.000 claims description 4
- 229940114072 12-hydroxystearic acid Drugs 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 claims description 2
- 239000003899 bactericide agent Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 claims description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000000976 ink Substances 0.000 description 44
- 229920005765 JONCRYL® HPD Polymers 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001148659 Panicum dichotomiflorum Species 0.000 description 2
- 229920005578 aromatic polyanhydride Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 229920005771 JONCRYL® HPD 296 Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002357 osmotic agent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007921 spray 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
- C09D11/30—Inkjet printing inks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention provides thermal foaming ink with excellent adhesion and a preparation method and application thereof, wherein the thermal foaming ink comprises the following components in percentage by mass: styrene-acrylic resin: 2 to 15 percent; dye or pigment: 2 to 15 percent; silicone-based auxiliary agent: 0.01 to 1.0 percent; solvent: 70 to 95.98 percent. The thermal foaming ink is based on a solvent-based system (e.g., ethanol as the primary solvent). The thermal foaming ink has strong adhesion with a base material, and particularly has excellent adhesion on a base material with low surface tension (such as a BOPP film); in addition, the printed handwriting is clear, has good adhesive force and is resistant to wiping; meanwhile, the ink has comprehensive printing performance which the thermal foaming ink should meet.
Description
Technical Field
The invention belongs to the technical field of printing ink, and particularly relates to thermal foaming ink with excellent adhesion and a preparation method and application thereof.
Background
The thermal foaming jet printing technology is a printing technology invented by the U.S. Hewlett packard company, and the main working principle is that ink is heated instantly inside a spray head, bubbles are generated after heating, the ink is sprayed out by the pressure of the bubbles, and the movement of an object to be jet printed is matched for imaging. The inks used in this printing process are collectively called thermal foaming inks, and are required to have smoothness of printing, intermittent printing performance, no clogging, resistance to wiping after printing, durability, and the like. Generally, the method is divided into solvent-based and water-based. The solvent thermal foaming ink generally uses ethanol and ketone as main solvents, and the water thermal foaming ink uses water as a main solvent.
At present, researchers have conducted extensive research on water, which is a non-toxic and harmless characteristic of a solvent, but the existing water-based thermal foaming ink generally has the problems that contact with the surface of a substrate is not firm, adhesion between the ink and the substrate is low, printed products are prone to falling off, and the like.
Disclosure of Invention
In order to improve the defects of the prior art, the invention provides a solvent type thermal foaming ink with excellent adhesion, a preparation method and application thereof, wherein the thermal foaming ink has excellent adhesion and is particularly suitable for BOPP film (biaxially oriented polypropylene film) substrates. Meanwhile, the thermal foaming ink also has excellent printing performance, such as fluency, no blockage, good scratch resistance, high gloss, water resistance and the like.
The invention is realized by the following technical scheme:
a solvent thermal foaming ink, which comprises the following components in percentage by mass:
styrene-acrylic resin: 2 to 15 percent;
dye or pigment: 2 to 15 percent;
silicone-based auxiliary agent: 0.01 to 1.0 percent;
solvent: 70 to 95.98 percent.
According to the invention, the ink comprises the following components in percentage by mass:
styrene-acrylic resin: 4 to 10 percent;
dye or pigment: 4 to 10 percent;
silicone-based auxiliary agent: 0.01 to 0.5 percent;
solvent: 80 to 92 percent.
According to the invention, the mass fraction of the styrene-acrylate resin is 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%; the styrene-acrylate resin has good film forming property, has strong adhesion with a base material (especially a low surface tension base material such as a BOPP film) and can realize the preparation of the high-adhesion thermal foaming ink.
According to the present invention, the styrene-acrylate resin has a structure represented by formula (I):
in the formula (I), x is an integer of 1-300, y is an integer of 0-300, z is an integer of 0-300, and y + z is more than or equal to 1; m is the same or different and is independently selected from H or methyl; r is C 1-20 Alkyl group of (1).
Preferably, y is an integer from 1 to 300. z is an integer of 1 to 300.
Preferably, R is C 4-20 Is preferably C 8-20 Straight-chain or branched alkyl, e.g. C 10-20 Linear or branched alkyl groups of (a).
According to the present invention, the styrene-acrylate-based resin has a number average molecular weight of 1000 to 30000, for example 1500 to 20000, for example 1800 to 15000; the glass transition temperature Tg of the styrene-acrylate resin is 50-80 ℃.
According to the present invention, the styrene-acrylic ester-based resin may be added to the ink in the form of a solid or in the form of an aqueous solution of an ammonium salt or a sodium salt thereof. If a solid form of the styrene-acrylate resin is used, the solid form of the styrene-acrylate resin may be neutralized with an aqueous NaOH solution and dissolved in a solvent to form a solution, which is then added.
According to the present invention, the styrene-acrylic resin may be a CSE series such as CSE-1000, CSE-2000, CSE-3000, etc., manufactured by Showa corporation, japan. Further, the Joncryl HPD series available from BASF corporation, for example, joncryl HPD 296, joncryl HPD 396, joncryl HPD 496 and the like may be used. It may also be Afuron 5022, which contains a side chain group (R group in formula (I)) containing 20 carbon atoms and has a number average molecular weight of about 14000.
According to the invention, the mass fraction of the dye or pigment is 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%; the addition of the dye or pigment can prepare inks of different colors.
According to the present invention, the dye or pigment may be selected according to the color of the ink, and illustratively, the dye is selected from various dyes conventionally used in the ink field, manufactured by BASF corporation, clariant corporation, germany, and the like. The pigment is selected from black PB1 and PB7; CABOT products in the United states: CAB-O-JET300, CAB-O-JET400; blue PB15, PB15:3; red PV19, PR122, PV23, PV37; pigment green c.i.p.g. 7, c.i.p.g.36; and so on.
According to the invention, the mass fraction of the silicone auxiliary agent is 0.01%, 0.02%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1.0%; the polysiloxane auxiliary agent plays a role in wetting and moisturizing, and can improve the smoothness of ink printing, the non-drying property and the wetting property of ink to a base material.
According to the invention, the silicone adjuvant is selected from alkyl or polyether modified siloxanes. Illustratively, the silicone based adjuvant is selected from BYK307, BYK323, BYK333, and the like, available from BYK corporation, germany; examples of such compounds are produced by Meiji corporation of America, such as Silwet L-7001, L-7600, L-7622, etc.; such as Megafac R-47 manufactured by Nippon DIC corporation.
According to the invention, the mass fraction of the solvent is 70%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 90%, 91%, 92%, 93%, 94%, 95% or 95.98%; the introduction of the solvent can well disperse other components uniformly, prepare the ink with better comprehensive performance and improve the adhesive force between the ink and the surface of the base material.
According to the invention, the solvent is selected from one or more of ethanol, water, acetone, butanone, cyclohexanone, butyl acetate, propylene glycol methyl ether acetate (PMA); preferably, the solvent is selected from one or more of ethanol, acetone, butanone, cyclohexanone, butyl acetate and propylene glycol methyl ether; also preferably, the solvent is selected from a mixed system of ethanol, water, acetone, cyclohexanone and propylene glycol methyl ether acetate. Illustratively, in the solvent, the mass percent of cyclohexanone is 10wt%, the mass percent of PMA is 2wt%, the mass percent of acetone is 5wt%, the mass percent of water is 3wt%, and the balance is ethanol, where the defined ink component content is one hundred percent.
According to the invention, the ink also comprises a polyester-based adjuvant: 0.01 to 1.0 percent.
According to the invention, the mass fraction of the polyester-based auxiliary agent is 0.01%, 0.02%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1.0%.
According to the invention, the polyester-based auxiliary agent is selected from polyester-based adhesion promoters, preferably, the polyester-based adhesion promoter is prepared from a composition comprising the following components: dimerized rosin, polyhydric fatty alcohols, hydroxy fatty acids, and anhydrides.
According to the invention, the composition comprises the following components in percentage by mass:
dimerized rosin: 2 to 10 percent; polyhydric fatty alcohol: 20 to 50 percent; hydroxy fatty acid: 20 to 50 percent; acid anhydride: 3 to 30 percent.
According to the invention, the polyol may be Priplast 3174, produced by university of bluegrass, uk.
According to the invention, the hydroxy fatty acid is selected from one or a mixture of two of 12-hydroxystearic acid or castor oil fatty acid.
According to the invention, the anhydride is chosen from aromatic polyanhydrides, for example from trimellitic anhydride and the like.
According to the invention, the ink also comprises other auxiliaries: 0 to 2 percent.
According to the invention, the other auxiliary agents are selected from one or more of a drier, a bactericide, an acid-base regulator, an osmotic agent and the like. Wherein the drier is selected from ZnO 1# manufactured by BASF corporation; tyzor A titanium drier manufactured by Dupont.
The invention provides a polyester adhesion promoter for thermal foaming ink, which is prepared from a composition comprising the following components: dimerized rosin, polyhydric fatty alcohols, hydroxy fatty acids, and anhydrides.
According to the invention, the accelerator is prepared from the composition by polymerization.
According to the invention, the number average molecular weight of the accelerator is between 1000 and 10000, most preferably between 2000 and 5000.
According to the invention, the composition comprises the following components in percentage by mass:
dimerized rosin: 2 to 10 percent; polyhydric fatty alcohol: 20 to 50 percent; hydroxy fatty acid: 20 to 50 percent; acid anhydride: 3 to 30 percent.
According to the invention, the polyol may be Priplast 3174, produced by university of bluegrass, uk.
According to the invention, the hydroxy fatty acid is selected from one or a mixture of two of 12-hydroxystearic acid or castor oil fatty acid.
According to the invention, the anhydride is chosen from aromatic polyanhydrides, for example from trimellitic anhydride and the like.
The invention also provides a preparation method of the polyester adhesion promoter, which comprises the following steps:
mixing dimerized rosin, polyhydric fatty alcohol and hydroxy fatty acid, and performing esterification reaction;
and after the esterification reaction is finished, adding acid anhydride for acidification treatment to obtain the polyester adhesion promoter.
According to the invention, the temperature of the esterification reaction is in the range of 140 to 180 ℃ (e.g., 140, 150, 160, 170 or 180 ℃). Preferably, the polyhydric fatty alcohol and the hydroxy fatty acid are added, the dimerized rosin is added after the polyhydric fatty alcohol and the hydroxy fatty acid are heated to a certain temperature (for example, 80-100 ℃), and then the dimerized rosin is continuously heated to a set temperature to perform the esterification reaction.
According to the invention, the temperature of the acidification reaction is between 100 and 140 ℃ (for example 100, 110, 120, 130 or 140 ℃).
The invention also provides a preparation method of the thermal foaming ink, which comprises the following steps:
mixing styrene-acrylate resin, dye or pigment, polysiloxane auxiliary agent, solvent and optionally polyester auxiliary agent and optionally other auxiliary agent to prepare the thermal foaming ink.
According to the invention, the method comprises the following steps:
fully dissolving styrene-acrylate resin in sodium hydroxide ethanol water solution to form resin solution; then adding the pigment or the dye, other solvents, the polysiloxane auxiliary agent, and optionally the polyester auxiliary agent and optionally other auxiliary agents in sequence, and uniformly mixing.
Exemplarily, the method specifically comprises the following steps:
adding sodium hydroxide into a mixed solution of ethanol and water, adjusting the pH value to 8.5, keeping the temperature at 55 ℃ under heating, and slowly adding solid styrene-acrylate resin until the solid styrene-acrylate resin is fully dissolved; cooling to room temperature to form a resin solution;
then adding the pigment or the dye, other solvents, the polysiloxane auxiliary agent, and optionally the polyester auxiliary agent and optionally other auxiliary agents in sequence, and uniformly mixing.
The invention also provides application of the thermal foaming ink, which is used for thermal foaming printing.
An article prepared by printing the above thermally foamable ink on a substrate.
According to the invention, the substrate is a low surface tension substrate, such as a BOPP substrate.
The invention has the beneficial effects that:
the invention provides thermal foaming ink with excellent adhesion and a preparation method and application thereof, wherein the thermal foaming ink comprises the following components in percentage by mass: styrene-acrylic resin: 2 to 15 percent; dye or pigment: 2 to 15 percent; silicone-based auxiliary agent: 0.01 to 1.0 percent; solvent: 70 to 95.98 percent. The thermal foaming ink is based on a solvent-based system (e.g., ethanol as the primary solvent). The thermal foaming ink has strong adhesion with a base material, and particularly has excellent adhesion on a base material with low surface tension (such as a BOPP film); in addition, the printed handwriting is clear, has good adhesive force and is resistant to wiping; meanwhile, the ink has comprehensive printing performance which the thermal foaming ink should meet.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Preparation example 1
Preparing a polyester adhesion promoter:
the content (mass percent) of each component in the composition for preparing the polyester adhesion promoter is as follows:
dimerized rosin: 5.00 percent
Polyhydric fatty alcohol (Priplast 3174): 40.00 percent
Castor oil fatty acid: 48.00 percent
Trimellitic anhydride: 7.00 percent.
Mixing Priplast 3174 and castor oil fatty acid in a four-mouth bottle, introducing nitrogen for protection, heating to 160 ℃, adding dimerized rosin when the temperature reaches 90 ℃, and continuing heating until the dimerized rosin is completely dissolved in the system. When the temperature reaches 160 ℃, the vacuum is started to remove water, and the reaction lasts for 6 hours. Cooling to 120 ℃, adding trimellitic anhydride solid until the system is clear and transparent, continuing to react for 2 hours, and cooling to room temperature to obtain the polyester adhesion promoter which is light brown viscous liquid.
This product can be dissolved in propylene glycol methyl ether acetate PMA to give a 50% solids solution.
Example 1
In a mixture of ethanol and water, sodium hydroxide was added, pH =8.5 was adjusted, temperature was maintained at 55 ℃ under heating, and styrene-acrylate resin (solid form) was slowly added until it was sufficiently dissolved. Cooled to room temperature to form a resin solution. The pigment or dye, the solvent, optionally the polyester adhesion promoter and optionally other additives are mixed in sequence and mixed evenly, and the specific mixture ratio is shown in table 1.
TABLE 1
The mixed ink was placed overnight, filtered, and poured into a Hewlett packard cartridge. After 24h the test was printed on a BOPP film and after the writing was dry, the finger was slid to evaluate the writing adhesion, the test scoring criteria and results are shown in table 2. The results in table 2 were rated between 1 and 10, with 1 being the worst and 10 being the best.
TABLE 2
| Formulation No. 1 | Formulation No. 2 | Ratio 3 | Ratio 4 | |
| Fluency of printing | Jia | Jia | Jia | Jia |
| Intermittent 0.5 second printing | PASS | PASS | PASS | PASS |
| Intermittent 1 second printing | PASS | PASS | PASS | PASS |
| Definition of handwriting | 7 | 9 | 9 | 10 |
| Drying time/second | 3-5 | 3-5 | 3-5 | 4-6 |
| Adhesion force | 4 | 8 | 8 | 10 |
| Water resistance | 5 | 10 | 10 | 10 |
From the above-mentioned proportioning test results, compared with the single resin CSE-1000, the single resin Arufon5022 has better film forming property and substrate adhesion, and it is obvious from formulas 1 and 3 that the selection of the resin has a great influence on the adhesion of the ink.
It can be seen from formulas 1 and 2, or from formulas 3 and 4 that after the polyester-based auxiliary agent prepared as described above is added, formula 2 is further improved as compared with formula 1, formula 4 is also further improved as compared with formula 2, and the clarity of writing is also improved, because it is related to the stability of dye or pigment assisted by ester bond in the polyester-based auxiliary agent. Meanwhile, due to the hydrophobic property of the polyester, the water resistance of the handwriting printed by the ink is improved.
In conclusion, the technical scheme of the invention can greatly improve the adhesion force of the printed handwriting of the hot bubble ink, and meanwhile, the polyester-based auxiliary agent can effectively further improve the adhesion force between the fonts printed by the ink and the base material.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (24)
1. A solvent thermal foaming ink, wherein the ink consists of the following components in percentage by mass:
styrene-acrylic ester resin: 2 to 15 percent;
dye or pigment: 2 to 15 percent;
silicone-based auxiliary agent: 0.01 to 1.0 percent;
solvent: 70-95.98%;
polyester-based auxiliary agent: 0.01 to 1.0 percent;
other auxiliary agents: 0 to 2 percent;
the other auxiliary agents are selected from one or more of a drier, a bactericide, an acid-base regulator and a penetrant; wherein the drier is selected from ZnO 1# manufactured by BASF company, or Tyzor AA-75 titanium drier manufactured by Dupont company;
wherein the polysiloxane auxiliary agent is selected from alkyl or polyether modified siloxane;
the polyester auxiliary agent is selected from polyester adhesion promoters, and the polyester adhesion promoters are prepared from a composition comprising the following components in percentage by mass:
dimerized rosin: 2 to 10 percent; polyhydric fatty alcohol: 20 to 50 percent; hydroxy fatty acid: 20 to 50 percent; acid anhydride: 3 to 30 percent.
2. The ink according to claim 1, wherein the ink comprises the following components in percentage by mass:
styrene-acrylic resin: 4 to 10 percent;
dye or pigment: 4 to 10 percent;
silicone-based auxiliary agent: 0.01 to 0.5 percent;
solvent: 80-92 percent;
polyester-based auxiliary agent: 0.01 to 1.0 percent;
other auxiliary agents: 0 to 2 percent;
the sum of the mass fractions of the components in the ink is one hundred percent.
3. The ink according to claim 1 or 2, wherein the styrene-acrylic resin has a structure represented by formula (I):
formula (I)
In the formula (I), x is an integer of 1-300, y is an integer of 0-300, z is an integer of 0-300, and y + z is more than or equal to 1; m, which are identical or different, are independently of one another selected from H or methyl; r is C 1-20 Alkyl group of (1).
4. An ink according to claim 3, in which y is an integer from 1 to 300; z is an integer from 1 to 300; r is C 4-20 Linear or branched alkyl groups of (a).
5. The ink according to claim 3, wherein the styrene-acrylic resin has a number average molecular weight of 1000 to 30000; the glass transition temperature Tg of the styrene-acrylate resin is 50-80 ℃.
6. The ink according to claim 1, wherein the silicone-based auxiliary agent is selected from BYK307, BYK323 or BYK333, manufactured by BYK, germany; silwet L-7001, L-7600 or L-7622, manufactured by Meiji corporation, USA; megafac R-47 manufactured by Nippon DIC corporation.
7. Ink according to claim 1, wherein the solvent is selected from one or more of ethanol, water, acetone, butanone, cyclohexanone, butyl acetate, propylene glycol methyl ether acetate (PMA).
8. The ink according to claim 7, wherein the solvent is selected from one or more of ethanol, acetone, butanone, cyclohexanone, butyl acetate, propylene glycol methyl ether.
9. The ink according to claim 7, wherein the solvent is selected from a mixed system of ethanol, water, acetone, cyclohexanone, propylene glycol methyl ether acetate.
10. The ink according to claim 9, wherein the solvent contains 10wt% of cyclohexanone, 2wt% of propylene glycol methyl ether acetate, 5wt% of acetone, 3wt% of water, and the balance ethanol, and the ink has a component content of one hundred percent.
11. The ink of claim 1, wherein the polyhydric fatty alcohol is Priplast 3174 manufactured by proctos co.
12. The ink of claim 1, wherein the hydroxy fatty acid is selected from one or a mixture of two of 12-hydroxystearic acid or castor oil fatty acid.
13. The ink according to claim 1, wherein the anhydride is selected from trimellitic anhydride.
14. The ink according to claim 1, wherein the polyester-based adhesion promoter has a number average molecular weight of 1000 to 10000.
15. The ink according to claim 1, wherein the polyester-based adhesion promoter is prepared by a method comprising the steps of:
mixing dimerized rosin, polyhydric fatty alcohol and hydroxy fatty acid, and carrying out esterification reaction;
and after the esterification reaction is finished, adding acid anhydride for acidification treatment to obtain the polyester adhesion promoter.
16. An ink according to claim 15, wherein the temperature of the esterification reaction is 140-180 ℃.
17. The ink according to claim 15, wherein the polyhydric fatty alcohol and the hydroxy fatty acid are added, and the mixture is heated to 80 to 100 ℃ and then the dimerized rosin is added, and then the mixture is further heated to a predetermined temperature to perform the esterification reaction.
18. The ink of claim 15, wherein the temperature of the acidification reaction is 100-140 ℃.
19. A method of preparing a thermally foamable ink according to any one of claims 1 to 18, wherein the method comprises the steps of:
mixing styrene-acrylate resin, dye or pigment, polysiloxane auxiliary agent, solvent, polyester auxiliary agent and other auxiliary agents to prepare the thermal foaming ink.
20. A method of preparing a thermally foamable ink according to claim 19, the method comprising the steps of:
fully dissolving styrene-acrylate resin in sodium hydroxide ethanol water solution to form resin solution; then adding the pigment or dye, other solvents, the polysiloxane auxiliary agent, the polyester auxiliary agent and other auxiliary agents in sequence, and mixing uniformly.
21. The method of preparing a thermal foaming ink of claim 20, the method comprising in particular the steps of:
adding sodium hydroxide into a mixed solution of ethanol and water, adjusting the pH value to 8.5, keeping the temperature at 55 ℃ under heating, and slowly adding solid styrene-acrylate resin until the solid styrene-acrylate resin is fully dissolved; cooling to room temperature to form a resin solution;
then adding the pigment or dye, other solvents, the polysiloxane auxiliary agent, the polyester auxiliary agent and other auxiliary agents in sequence, and mixing uniformly.
22. Use of a thermal foaming ink according to any one of claims 1 to 18 for thermal foaming printing.
23. An article made by printing the thermally foamable ink of any one of claims 1 to 18 on a substrate.
24. The article of claim 23, wherein the substrate is a biaxially oriented polypropylene substrate.
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| US4260531A (en) * | 1979-07-02 | 1981-04-07 | A. B. Dick Company | Ink composition for printing on polyolefin |
| CN101831215A (en) * | 2010-04-28 | 2010-09-15 | 王学珍 | High-performance jet ink |
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