CN111808293B - Polyhydroxy polyester carboxylic acid polymer for preparing solvent type thermal foaming ink - Google Patents
Polyhydroxy polyester carboxylic acid polymer for preparing solvent type thermal foaming ink Download PDFInfo
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- CN111808293B CN111808293B CN201910290618.9A CN201910290618A CN111808293B CN 111808293 B CN111808293 B CN 111808293B CN 201910290618 A CN201910290618 A CN 201910290618A CN 111808293 B CN111808293 B CN 111808293B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- 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
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Abstract
A polyhydroxy polyester carboxylic acid polymer for use in the preparation of solvent-based, thermally foamable inks, said polyhydroxy polyester carboxylic acid polymer starting from a branched polyhydroxy polyester oligomer as a core containing a portion of the hydroxyl groups reacted with trimellitic anhydride to provide carboxylic acid groups, a portion of the hydroxyl groups reacted with caprolactone to form polyester segments containing hydroxyl groups at the ends; the polyhydroxy polyester carboxylic acid polymer may also undergo a polyether reaction with an alkylene oxide to adjust the hydrophilicity and crystallinity of the polymer to make it more readily adaptable for use in a thermally foamable ink composition. The polyhydroxy polyester carboxylic acid polymer is added into a mixed system which takes ethanol as a main solvent, so that the continuous printing performance of the ink can be enhanced; the adhesive force of the solvent type thermal foaming ink taking ethanol as a main solvent to a base material is improved, and particularly, the adhesive force on the base material with low surface tension is excellent; 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 a polyhydroxy polyester carboxylic acid polymer for preparing solvent type thermal foaming ink, and a preparation method and application thereof.
Background
The thermal foaming jet printing technology is a printing technology invented by the American Hewlett packard company, and the main working principle is that ink is heated instantly in a nozzle, bubbles are generated after heating, the ink is jetted out by the pressure of the bubbles, and the motion 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, and meanwhile the existing thermal foaming ink is poor in continuous printing performance and difficult to achieve continuous printing.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a polyhydroxy polyester carboxylic acid polymer for preparing solvent type thermal foaming ink and a preparation method and application thereof on one hand, and provides thermal foaming ink comprising the polyhydroxy polyester carboxylic acid polymer and a preparation method and application thereof on the other hand; the thermal foaming ink has excellent adhesion and continuous printing performance, and is particularly suitable for BOPP film (biaxially oriented polypropylene film) base materials. 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 polyhydroxypolyester carboxylic acid polymer, wherein the polyhydroxypolyester carboxylic acid polymer is obtained by polymerizing a composition comprising the following components in parts by mass:
(1) branched polyhydroxy polyester oligomer as a parent nucleus; 10 to 70 percent;
(2) trimellitic anhydride; 5 to 20 percent;
(3) caprolactone; 20 to 40 percent.
According to the invention, the composition also comprises at least one of the following components in percentage by mass:
(4) a catalyst; 0.01-2%;
(5) an alkylene oxide; 0 to 65 percent;
(6) an auxiliary agent; 0 to 2 percent.
According to the invention, the mass fraction of branched polyhydroxy polyester oligomer as parent nucleus is 10%, 15%, 20%, 30%, 40%, 50%, 60% or 70%. The branched polyhydroxy polyester oligomer is a mother core, wherein partial hydroxyl can be subjected to polymerization reaction with anhydride in trimellitic anhydride.
According to the invention, the branched polyhydroxy polyester oligomer is an oligomer of polyhydroxy monocarboxylic acid monomers having a "dendritic" polyester structure with at least 4 hydroxyl groups or more. Depending on the degree of polymerization and the number of "dendritic branches", the hydroxyl groups may be more than 4, more than 8, more than 16, more than 32 or more.
For example, the branched polyhydroxy polyester oligomer has a structure shown in formula (1) or formula (2),
wherein, the number of the hydroxyl group of the structure shown in the formula (1) is 16, which can be defined as a medium-low branched structure, and the number of the hydroxyl group of the structure shown in the formula (2) is more than 32, which can be defined as a multi-branched structure.
According to the invention, the branched polyhydroxy polyester oligomer may be prepared by methods known in the art or may be commercially available, for example from the Boltorn product series of Perstrop, such as Boltorn H311, Boltorn W3000, Bolton P500 and Boltoron P1000. Preferably Boltorn P500 and Boltorn W3000, said Boltorn P500 being itself soluble in polyether polyols, having a molecular weight of 1800 and an average of about 16 hydroxyl groups per parent core; the Boltorn W3000 is itself soluble in polyether polyols, has a molecular weight of 9000, and has an average of about 32 hydroxyl groups per parent nucleus.
According to the invention, the mass fraction of trimellitic anhydride is 5%, 8%, 10%, 12%, 15%, 16%, 18% or 20%. When the temperature reaches above 120 ℃, the acid anhydride in the trimellitic anhydride can open the ring and react with the active hydroxyl groups from the branched polyhydroxy polyester oligomer to form free carboxylic acid.
According to the invention, the structural formula of the trimellitic anhydride is shown as formula 3:
according to the invention, the molar ratio of the total hydroxyl groups in the trimellitic anhydride and the branched polyhydroxy polyester oligomer is from 0.5 to 6:10, for example from 2 to 4:10, i.e. from 5 to 60% of the hydroxyl groups in the branched polyhydroxy polyester oligomer are reacted with the anhydride. The rest hydroxyl in the branched polyhydroxy polyester oligomer and caprolactone are subjected to ring-opening polymerization reaction to generate a hydroxyl-terminated polycaprolactone polymer, and the molecular weight is increased.
According to the invention, the mass fraction of the catalyst 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%, 1.0%, 1.5% or 2%.
According to the invention, the catalyst is chosen from catalysts which can catalyze the ring-opening addition reaction of caprolactone and hydroxyl groups, such as dibutyl tin Dilaurate (DBTL), tetrabutyl zirconate (DBZr) and tetrabutyl phthalate (DBTi). Tetrabutylzirconate (DBZr) and tetrabutylphthalate (DBTi) are preferred.
According to the invention, the alkylene oxide may be, for example, ethylene oxide and/or propylene oxide.
According to the invention, the alkylene oxide is present in a mass fraction of 0%, 5%, 10%, 20%, 30%, 40%, 50%, 60% or 65%. Illustratively, the mass fraction of the ethylene oxide is 0 to 60%, and the mass fraction of the propylene oxide is 0 to 20%.
According to the invention, the auxiliary is selected from other catalysts, antioxidants or UV protection auxiliaries and the like.
According to the invention, the mass fraction of the 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%, 1.0%, 1.5% or 2%.
According to the invention, the polyhydroxypolyester carboxylic acid polymer is a yellow waxy solid.
According to the invention, the polyhydroxy polyester carboxylic acid polymer can be dissolved in propylene glycol methyl ether acetate (PMA) or butyl acetate to prepare a solution with a certain mass concentration for use.
The present invention also provides a method for preparing the above-mentioned polyhydroxypolyester carboxylic acid polymer, comprising the steps of:
the polyhydroxy polyester carboxylic acid polymer is prepared by reacting branched polyhydroxy polyester oligomer serving as a mother core, trimellitic anhydride, caprolactone and optional catalyst, and optional alkylene oxide and optional auxiliary agent.
According to the invention, the method comprises the following steps:
1) dissolving branched polyhydroxy polyester oligomer serving as a parent nucleus in an organic solvent, adding trimellitic anhydride, and reacting;
2) adding a caprolactone monomer, a catalyst and an optional auxiliary agent into the mixed system obtained in the step 1), and reacting to prepare the polyhydroxy polyester carboxylic acid polymer.
According to the invention, the method further comprises the steps of:
3) mixing the product obtained in the step 2) with epoxy cyclic hydrocarbon, and carrying out a polyether esterification reaction to obtain the polyether modified polyhydroxy polyester carboxylic acid polymer.
According to the invention, in step 1), the organic solvent is toluene or xylene.
According to the invention, in step 1), the reaction temperature is between 80 and 130 ℃. The reaction was carried out under nitrogen protection. After the reaction is completed, the organic solvent is preferably removed. The organic solvent is preferably removed by distillation under reduced pressure.
According to the invention, step 1) comprises the following steps:
dissolving branched polyhydroxy polyester oligomer in an organic solvent, heating to 80 ℃, adding trimellitic anhydride powder, fully stirring, continuously heating to 125 ℃, keeping constant temperature, maintaining nitrogen protection in the whole process until a clear and transparent solution is obtained, cooling to 80 ℃, keeping reduced pressure distillation in the process, and removing the organic solvent.
According to the invention, in step 2), the temperature of the reaction is 160-200 ℃, the reaction is carried out until all caprolactone monomers are reacted, for example, the reaction time is 6-12 hours.
In the present invention, the polyhydroxy polyester carboxylic acid polymer (i.e. the product of step 2) contains carboxylic acid and active hydroxyl, which can be further polymerized with alkylene oxide (e.g. ethylene oxide and/or propylene oxide) to form polyether structure, the polyhydroxy polyester carboxylic acid polymer with polyether structure has the basic characteristics of surfactant and hydrophilic polar segment, especially the ethylene oxide and/or propylene oxide polymer has lower melting point, and the polyether modified polyhydroxy polyester carboxylic acid polymer has better solubility and solvent compatibility.
Preferably, the alkylene oxide is selected from at least one of ethylene oxide and propylene oxide, for example propylene oxide is used in an amount not exceeding 1/3 the amount of ethylene oxide. For example, 0 to 60%, preferably 5 to 30%, of ethylene oxide forms EO polyether chains.
The invention also provides the use of the above-mentioned polyhydroxy polyester carboxylic acid polymer as an additive for thermal foaming inks. In particular, it acts as a humectant. For example, the amount of addition thereof to the thermally foamable ink is 2% or less.
According to the present invention, the thermal foaming ink added with the above-mentioned polyhydroxypolyester carboxylic acid polymer has excellent adhesion and continuous printing performance, and is particularly suitable for a BOPP film (biaxially oriented polypropylene film) substrate.
The invention also provides 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;
polymer auxiliary agent: 0.01 to 2.0 percent;
solvent: 70-95.98%;
the polymer auxiliary agent comprises the polyhydroxy polyester carboxylic acid polymer.
According to the invention, the thermal foaming ink comprises the following components in percentage by mass:
styrene-acrylic resin: 4 to 10 percent;
dye or pigment: 4 to 10 percent;
polymer auxiliary agent: 0.01 to 1.5 percent;
solvent: 80-92 percent;
the polymer auxiliary agent comprises the polyhydroxy polyester carboxylic acid polymer.
According to the invention, the polymer auxiliary agent also comprises a polysiloxane auxiliary agent.
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 C1-20Alkyl group of (1).
Preferably, y is an integer from 1 to 300. z is an integer of 1 to 300.
Preferably, R is C4-20Is preferably C8-20Straight-chain or branched alkyl, e.g. C10-20Linear or branched alkyl.
According to the invention, the number average molecular weight of the styrene-acrylate resin is 1000-30000, such as 1500-20000, such as 1800-15000; the glass transition temperature T of the styrene-acrylic resingIs 50-80 deg.C.
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-acrylic resin is used, the solid form of the styrene-acrylic 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 having 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 PB 7; CABOT products in the United states: CAB-O-JET300, CAB-O-JET 400; blue PB15, PB15: 3; red PV19, PR122, PV23, PV 37; pigment green c.i.p.g.7, c.i.p.g.36; food grade FD & C dyes such as FD & C red #3, FD & C red #40, ED & C yellow #5, FD & C yellow #6, FD & C blue #1 and FD & C green #3, and the like.
According to the invention, the mass fraction of the polyhydroxypolyester carboxylic acid polymer is 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.5% or 2%; the addition of the polyhydroxy polyester carboxylic acid polymer can enhance the hitching performance of the ink and promote the adhesion of the ink to the substrate surface.
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 increases the adhesion between the ink and the surface of the substrate, so that the smoothness of ink printing, the non-drying property and the wetting property of the ink to the substrate can be improved.
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 of Germany; such as Silwet L-7001, L-7600, L-7622, etc., manufactured by Meiji corporation, USA; 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.
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 also provides a preparation method of the thermal foaming ink, which comprises the following steps:
mixing styrene-acrylate resin, dye or pigment, polymer auxiliary agent, solvent and optionally other auxiliary agents according to the mass fraction to prepare the thermal foaming ink; wherein the polymer auxiliary agent comprises the polyhydroxy polyester carboxylic acid polymer.
According to the invention, the method comprises the following steps:
1) fully dissolving styrene-acrylate resin in sodium hydroxide ethanol water solution to form resin solution;
2) dissolving a polyhydroxy polyester carboxylic acid polymer in propylene glycol methyl ether acetate to form an auxiliary agent solution;
3) and uniformly mixing the resin solution, the auxiliary agent solution, the pigment or the dye, other solvents, the polysiloxane auxiliary agent and optionally other auxiliary agents.
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;
dissolving a polyhydroxy polyester carboxylic acid polymer in propylene glycol methyl ether acetate to form an auxiliary agent solution;
and uniformly mixing the resin solution, the auxiliary agent solution, the pigment or the dye, other solvents, the polysiloxane auxiliary agent and optionally other auxiliary agents.
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 a polyhydroxy polyester carboxylic acid polymer for preparing solvent-based thermal foaming ink, a preparation method and application thereof, wherein the polyhydroxy polyester carboxylic acid polymer is prepared by starting from branched polyhydroxy polyester oligomer serving as a parent nucleus, reacting partial hydroxyl contained in the polyhydroxy polyester oligomer with trimellitic anhydride to provide carboxylic acid groups, and reacting partial hydroxyl with caprolactone to form a polyester chain segment with a hydroxyl at the tail end; the polyhydroxy polyester carboxylic acid polymer can be further subjected to polyether reaction with alkylene oxide to obtain a polyether modified polyhydroxy polyester carboxylic acid polymer, so that the hydrophilicity and crystallinity of the polyhydroxy polyester carboxylic acid polymer are adjusted, and the polyhydroxy polyester carboxylic acid polymer is more easily adapted to a thermal foaming ink composition. The polyhydroxy polyester carboxylic acid polymer is added into a mixed system which takes ethanol as a main solvent, so that the continuous printing performance of the ink can be enhanced; the adhesive force of the solvent type thermal foaming ink taking ethanol as a main solvent to a base material is improved, and particularly, the adhesive force on the base material with low surface tension (such as a BOPP film) is excellent; 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
Mixing 50 parts by mass of Boltorn P500 into 50 parts by mass of xylene in a four-neck flask, heating to 80 ℃, adding 22 parts by mass of trimellitic anhydride powder, fully stirring, continuously heating to 125 ℃ and keeping constant temperature, keeping nitrogen protection in the whole process until a clear and transparent solution is obtained, cooling to 80 ℃, keeping reduced pressure distillation in the process, and removing the xylene. Adding 27.8 parts by mass of caprolactone monomer and 0.2 part by mass of tetrabutyl phthalate, heating to 180 ℃, reacting for 8 hours until all caprolactone monomers are reacted (no caprolactone monomer is detected by gas chromatography), obtaining polyhydroxy polyester carboxylic acid polymer, namely PCCCA-1 which is light yellow waxy solid, wherein the product can be dissolved in PMA (propylene glycol methyl ether acetate) to form a 20 wt% solution for convenient use.
Preparation example 2
50 parts by mass of PCCCA-1 prepared in preparation example 1, 40 parts by mass of ethylene oxide and 10 parts by mass of propylene oxide are subjected to a polyether esterification reaction to obtain a polyether modified polyhydroxy polyester carboxylic acid polymer which is marked as PCCCA-1-EO/PO, and the product is a light yellow semi-waxy solid which is dissolved in PMA to form a 30% solution for convenient use.
Preparation example 3
In a four-neck flask, 68 parts by mass of Boltorn W3000 is mixed into 24.8 parts by mass of caprolactone, the temperature is increased to 80 ℃, 7 parts by mass of trimellitic anhydride powder is added, the mixture is fully stirred, 0.2 part by mass of tetrabutyl phthalate is added when the temperature is 120 ℃, the temperature is continuously increased to 160 ℃ and is kept constant, nitrogen protection is kept in the whole process, the reaction is carried out for 8 hours until all caprolactone monomers are completely reacted (no caprolactone monomer is detected by gas chromatography), a polyhydroxy polyester carboxylic acid polymer is obtained, which is marked as PCCCA-2, is a yellow waxy solid, can be dissolved in PMA (propylene glycol methyl ether acetate), and becomes a 20% solution for convenient use.
Example 1
To a mixture of ethanol and water, sodium hydroxide was added, the pH was adjusted to 8.5, the temperature was maintained at 55 ℃ under heating, and styrene-acrylate resin Aurfon 5022 (in solid form) was slowly added until it was sufficiently dissolved. Cooled to room temperature to form a resin solution. The dye, BYK307 and other solvents are mixed in sequence, the polyhydroxy polyester carboxylic acid polymer or polyether modified polyhydroxy polyester carboxylic acid polymer prepared in the preparation example is uniformly mixed, the rotating speed is 1000rpm, after fully mixing for 30 minutes, the drier is added and mixed for 5 minutes, and the specific ratio is shown in Table 1.
TABLE 1
The mixed ink was placed overnight, filtered, and poured into a Hewlett packard cartridge. After 24h, printing test is carried out on the BOPP film, the process is monitored, the continuous printing performance is evaluated, after the handwriting is dried, the adhesion of the handwriting is evaluated by finger sliding, and the test scoring standard and the result are shown in the 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 2-0 | Formulation 2-1 | Formulation 2-2 | Formulations 2 to 3 | |
| Fluency of printing | Difference (D) | Jia | Jia | Jia |
| Intermittent 0.5 second printing | X | PASS | PASS | PASS |
| Intermittent 1 second printing | X | PASS | PASS | PASS |
| Intermittent 2 second printing | X | X | X | PASS |
| Definition of handwriting | 8 | 9 | 8 | 10 |
| Drying time/second | 3-4 | 3-5 | 3-5 | 4-6 |
| Adhesion force | 6 | 8 | 10 | 9 |
| Water resistance | 10 | 10 | 9 | 9 |
The above examples show that when the polyhydroxy polyester carboxylic acid polymer additive of the present invention is added, the continuous printing performance and the adhesion are improved, and the print definition is improved to different degrees. And in the later storage experiment, the abnormality of the additive is not seen. Namely, the polyhydroxy polyester carboxylic acid polymer of the invention is used as a multifunctional additive to play a plurality of roles of enhancing continuous beating, improving adhesive force and the like in an ink formula.
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 within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (24)
1. Use of a polyhydroxy polyester carboxylic acid polymer, wherein it is used as an additive in a thermal foaming ink;
the polyhydroxy polyester carboxylic acid polymer is obtained by polymerizing a composition comprising the following components in parts by mass:
(1) branched polyhydroxy polyester oligomer as a parent nucleus; 10 to 70 percent;
(2) trimellitic anhydride; 5 to 20 percent;
(3) caprolactone; 20 to 40 percent;
the branched polyhydroxy polyester oligomer is an oligomer of polyhydroxy monocarboxylic acid monomers having a "dendritic" polyester structure of at least 16 hydroxyl groups or more.
2. The use according to claim 1, wherein the composition further comprises at least one of the following components in mass fraction:
(4) a catalyst; 0.01-2%;
(5) an alkylene oxide; 0 to 65 percent;
(6) an auxiliary agent; 0 to 2 percent.
3. Use according to claim 1, wherein the branched polyhydroxy polyester oligomer has up to 32 or more hydroxyl groups.
4. The use according to claim 1, wherein the branched polyhydroxy polyester oligomer has the structure according to formula (1) or formula (2),
wherein, the number of the hydroxyl groups of the structure shown in the formula (1) is 16, and the structure is a mid-low branched structure; the structure shown in the formula (2) has a multi-branched structure, wherein the number of hydroxyl groups is more than 32.
5. Use according to claim 2, wherein the alkylene oxide is ethylene oxide and/or propylene oxide.
6. Use according to claim 5, wherein the mass fraction of ethylene oxide is 0-60% and the mass fraction of propylene oxide is 0-20%.
7. The use according to claim 1, wherein the polyhydroxypolyester carboxylic acid polymer is prepared by a preparation method comprising the steps of:
the polyhydroxy polyester carboxylic acid polymer is prepared by reacting branched polyhydroxy polyester oligomer serving as a mother core, trimellitic anhydride, caprolactone and optional catalyst, and optional alkylene oxide and optional auxiliary agent.
8. Use according to claim 7, wherein the method comprises the steps of:
1) dissolving branched polyhydroxy polyester oligomer serving as a parent nucleus in an organic solvent, adding trimellitic anhydride, and reacting;
2) adding a caprolactone monomer, a catalyst and an optional auxiliary agent into the mixed system obtained in the step 1), and reacting to prepare the polyhydroxy polyester carboxylic acid polymer.
9. Use according to claim 8, wherein the method further comprises the steps of:
3) mixing the product obtained in the step 2) with epoxy cyclic hydrocarbon, and carrying out a polyether esterification reaction to obtain the polyether modified polyhydroxy polyester carboxylic acid polymer.
10. Use according to claim 8, wherein step 1) comprises in particular the following steps:
dissolving branched polyhydroxy polyester oligomer in an organic solvent, heating to 80 ℃, adding trimellitic anhydride powder, fully stirring, continuously heating to 125 ℃, keeping constant temperature, maintaining nitrogen protection in the whole process until a clear and transparent solution is obtained, cooling to 80 ℃, keeping reduced pressure distillation in the process, and removing the organic solvent.
11. Use according to claim 8, wherein in step 2) the temperature of the reaction is 160-200 ℃.
12. A 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;
polymer auxiliary agent: 0.01 to 2.0 percent;
solvent: 70-95.98%;
the polymer aid comprising a polyhydroxy polyester carboxylic acid polymer in the use according to any of claims 1 to 11.
13. The thermally foamable ink of claim 12, wherein the thermally foamable ink comprises the following components in mass fraction:
styrene-acrylic resin: 4 to 10 percent;
dye or pigment: 4 to 10 percent;
polymer auxiliary agent: 0.01 to 1.5 percent;
solvent: 80-91 percent;
the polymer aid comprising a polyhydroxy polyester carboxylic acid polymer in the use according to any of claims 1 to 11.
14. The thermally foamable ink of claim 12 or 13, wherein the polymer adjuvant further comprises a silicone adjuvant.
15. The thermal foaming ink of claim 12 or 13, wherein the styrene-acrylate based 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 C1-20Alkyl group of (1).
16. The thermally foamable ink of claim 15, wherein y is an integer from 1 to 300; z is an integer of 1 to 300.
17. The thermally foamable ink of claim 15, wherein R is C4-20Linear or branched alkyl.
18. The thermally foamable ink of claim 17, wherein R is C8-20Linear or branched alkyl.
19. The thermally foamable ink of claim 18, wherein R is C10-20Linear or branched alkyl.
20. A method of making a thermal foaming ink according to any one of claims 12 to 19, the method comprising the steps of:
mixing styrene-acrylate resin, dye or pigment, polymer auxiliary agent, solvent and optionally other auxiliary agents according to the mass fraction to prepare the thermal foaming ink; wherein the polymer adjuvant comprises a polyhydroxy polyester carboxylic acid polymer in the use according to any of claims 1 to 11.
21. The method of manufacturing of claim 20, wherein the method comprises the steps of:
1) fully dissolving styrene-acrylate resin in sodium hydroxide ethanol water solution to form resin solution;
2) dissolving the polyhydroxy polyester carboxylic acid polymer in propylene glycol methyl ether acetate to form an auxiliary agent solution;
3) and uniformly mixing the resin solution, the auxiliary agent solution, the pigment or the dye, other solvents, the polysiloxane auxiliary agent and optionally other auxiliary agents.
22. An article made by printing the thermally foamable ink of any one of claims 12 to 19 on a substrate.
23. The article of claim 22, wherein the substrate is a low surface tension substrate.
24. The article of claim 22, wherein the substrate is a BOPP substrate.
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| US9000101B2 (en) * | 2013-07-10 | 2015-04-07 | Xerox Corporation | Anhydride end-capping of polymers |
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