CN113122122B - High-solid-content polyurethane ink resin, preparation method and application thereof - Google Patents

High-solid-content polyurethane ink resin, preparation method and application thereof Download PDF

Info

Publication number
CN113122122B
CN113122122B CN202110360669.1A CN202110360669A CN113122122B CN 113122122 B CN113122122 B CN 113122122B CN 202110360669 A CN202110360669 A CN 202110360669A CN 113122122 B CN113122122 B CN 113122122B
Authority
CN
China
Prior art keywords
ink resin
polyurethane ink
solid content
chain extender
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110360669.1A
Other languages
Chinese (zh)
Other versions
CN113122122A (en
Inventor
吴迪
贾海亭
何国平
雷生亮
张磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Beijing Co Ltd
Original Assignee
Wanhua Chemical Beijing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Beijing Co Ltd filed Critical Wanhua Chemical Beijing Co Ltd
Priority to CN202110360669.1A priority Critical patent/CN113122122B/en
Publication of CN113122122A publication Critical patent/CN113122122A/en
Application granted granted Critical
Publication of CN113122122B publication Critical patent/CN113122122B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Abstract

The invention discloses a high-solid content polyurethane ink resin, a preparation method and application thereof, wherein the resin is prepared by reacting the following raw materials in parts by mass: 28-46 parts of polymer polyol, 3-15 parts of polyisocyanate, 2-9 parts of functional amine chain extender E, 0.1-13 parts of functional end-capping reagent T and 30-60 parts of solvent. The polyurethane resin of the invention has lower viscosity and higher molecular weight when the solid content is more than 45 percent, and the prepared ink has excellent leveling property, adhesion fastness, anti-adhesion property and the like.

Description

High-solid-content polyurethane ink resin, preparation method and application thereof
Technical Field
The invention relates to the technical field of polyurethane ink resin, in particular to high-solid content polyurethane ink resin, a preparation method and application thereof.
Background
In the field of plastic flexible package printing in China, gravure printing occupies an absolutely dominating position due to the exquisite printing effect and high-efficiency printing efficiency. The inks used for gravure printing are classified into polyurethane inks, acrylic inks, chlorinated polypropylene inks, and polyamide inks, depending on the type of the main resin. The polyurethane ink has the characteristics of wide adaptation to base materials, integration of dry and light steaming and boiling, compound and universal surface printing and the like, is the key point of development and application of people, occupies over half market share of gravure ink, and is in rapid development.
GB38507-2020 imposes limits on Volatile Organic Compounds (VOCs) in various inks including intaglio inks, wherein the limit for solvent-based intaglio inks is 75% or less, the implementation of which will pose certain challenges for polyurethane inks currently on the market. On the other hand, with the rising awareness of environmental protection, high solid content and low viscosity ink is recognized as a practical and feasible technical route, and the development of high solid content and low viscosity resin is the key point.
In the past, people mainly pay attention to some basic performances such as substrate adhesion, printability, composite strength and the like in research on polyurethane ink resin, and reports are reported on how to realize high solid content and low viscosity of the resin. For example, in chinese patent CN103012724A, a large number of allophanate groups are introduced into the resin, so that the ink made of the resin has good adhesion fastness to substrates such as PET, NY, PP, etc. Chinese patent CN106928423A discloses a preparation method of polyester polyurethane resin, and the ink prepared by the preparation method has good composite strength and boiling resistance. European patent EP1743911A1 adopts a mode of blending high molecular weight polyurethane and low molecular weight polyurethane to improve the redissolution property of the ink so as to improve the printability, and meanwhile, the anti-blocking property, the adhesion fastness and the like are balanced by adjusting the proportion of the two.
In fact, the solid content of the resin of the prior art is generally below 35%, and if the solid content is increased to above 45%, the workability is lost due to the excessive viscosity. Because various properties of the polyurethane composite ink, such as pigment dispersibility, leveling property, anti-adhesion property, composite strength and the like, are closely related to the molecular weight of the resin, the molecular weight of the resin cannot be reduced for ensuring the ink performance, and when the molecular weight of the resin is not changed, the viscosity of the resin can be increased sharply along with the increase of the solid content of the resin, and even the fluidity is lost.
Therefore, the development of the polyurethane composite ink resin with complete performance, high solid content and low viscosity has practical urgency and application value, and the key point is how to reduce the viscosity of the resin and improve the solid content while ensuring the molecular weight of the resin.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a high-solid-content polyurethane ink resin, wherein a specially prepared functional amine chain extender E and a specially prepared functional amine chain extender T are introduced into a polyurethane resin, and the functional amine chain extender E and the functional amine chain extender T are synergistic to realize high solid content and low viscosity of the resin and have excellent application performance.
Still another object of the present invention is to provide a method for preparing such a high solid content polyurethane ink resin.
The invention also aims to provide the application of the high-solid-content polyurethane ink resin.
In order to realize the purpose, the invention adopts the following technical scheme:
the high-solid-content polyurethane ink resin is prepared by reacting the following raw materials in parts by mass: 28-46 parts of polymer polyol, 3-15 parts of polyisocyanate, 2-9 parts of functional amine chain extender E, 0.1-13 parts of functional end capping agent T and 30-60 parts of solvent.
In a specific embodiment, the functional amine chain extender E is formed by reacting an amine chain extender with tertiary glycidyl carbonate; preferably, the molar ratio of the amine chain extender to the tertiary carbonic acid glycidyl ester is 1: 0.1-1, and preferably 1: 0.3-0.8.
The amine chain extender is selected from primary amine or secondary amine containing at least two amine groups, preferably, the amine chain extender is selected from at least any one of isophorone diamine, ethylene diamine, propylene diamine, 1, 6-hexamethylene diamine, 1, 4-butylene diamine, neopentyl diamine, dicyclohexyl methane diamine, 1, 4-cyclohexene diamine, naphthylamine, ethylene diamine sodium ethanesulfonate, ethylene diamine sodium propanesulfonate and 2, 4-diaminobenzene sodium sulfonate; more preferably, the amine chain extender is selected from isophoronediamine or 1, 6-hexamethylenediamine.
Wherein the glycidyl versatate is selected from at least one of glycidyl pivalate, glycidyl neohexanoate, glycidyl neoheptanoate, glycidyl neooctanoate, glycidyl neononanoate, glycidyl neodecanoate, glycidyl neoundecanoate and glycidyl neotridecanoate; preferably, the glycidyl versatate is glycidyl neodecanoate.
In a specific embodiment, the functional blocking agent T is formed by reacting monohydroxy tertiary amine with lactone, and the number average molecular weight of the functional blocking agent T is 200-3000, preferably 400-2000.
Wherein the monohydroxy tertiary amine is at least one selected from the group consisting of monohydroxy tertiary amines having a hydroxyl group at one end and a tertiary amine at the other end, preferably N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanolamine, N, N-dimethylaminopropanol, N, N-diethylaminopropanol, N, N-dipropylaminopropanol, N, N-dibutylaminopropanol, N-ethyl-N-hydroxyethylaniline, N-benzyl-N-methylethanolamine, N, N-dimethylaminoethoxyethanol; more preferably, the monohydroxy tertiary amine is N, N-dimethylethanolamine or N, N-diethylethanolamine.
Wherein the lactone is an aliphatic cyclic lactone; preferably, the lactone is selected from at least any one of beta-propiolactone, gamma-butyrolactone, beta-butyrolactone, delta-valerolactone, gamma-valerolactone, epsilon-caprolactone, delta-caprolactone, gamma-heptolactone, omega-octalactone, delta-octalactone, gamma-octalactone, delta-nonalactone, gamma-nonalactone, delta-decalactone, gamma-undecalactone, delta-dodecalactone, gamma-dodecalactone, delta-tetradecanolide, 15-pentadecanolide, 16-hexadecanolide, glycolide, and lactides; more preferably, the lactone is selected from at least any one of delta-valerolactone, gamma-valerolactone, epsilon-caprolactone, delta-caprolactone and gamma-caprolactone.
In a particular embodiment, the polymer polyol is selected from polyester polyols or polyether polyols; preferably, the polymer polyol has a functionality of 2 to 3, preferably 2, and a number average molecular weight of 400 to 6000, preferably 1000 to 4000.
Wherein the polyester polyol is hydroxyl-terminated polyester polyol generated by polycondensation of dihydric alcohol and dibasic acid; the dihydric alcohol is at least one selected from ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, methyl propylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, neopentyl glycol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 1, 4-cyclohexyldiol, dihydroxydiphenyl sulfone, 2-bis (4-hydroxyphenyl) propane and 4, 4' -dihydroxydiphenyl methane; the dibasic acid is at least one selected from sebacic acid, adipic acid, azelaic acid, terephthalic acid, isophthalic acid and phthalic acid.
Wherein the polyether polyol is selected from polyether polyols obtained by polymerization of alkylene oxide by taking a hydroxyl compound as an initiator; preferably, the hydroxyl compound as the initiator is at least any one selected from the group consisting of propylene glycol, ethylene glycol, diethylene glycol, propylene glycol, 1, 3-propanediol, dipropylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, hexanediol, pentanediol, 3-methyl-1, 5-pentanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 12-dodecanediol, catechol, resorcinol, bisphenol F, and bisphenol a; the alkylene oxide is at least any one selected from ethylene oxide, propylene oxide and butylene oxide.
In a specific embodiment, the isocyanate is selected from at least any one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), 1, 4-cyclohexane diisocyanate (CHDI), cyclohexane dimethylene diisocyanate (HXDI), trimethyl-1, 6-hexamethylene diisocyanate (TMHDI), methylcyclohexyl diisocyanate (HTDI), preferably at least any one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI).
In a specific embodiment, the solvent is selected from one or more of ester, secondary alcohol and tertiary alcohol solvents; preferably one or more of ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate and isopropanol; more preferably one or more of ethyl acetate, n-propyl acetate and isopropanol.
In a specific embodiment, the solid content of the polyurethane ink resin is 40% to 70%, preferably 45% to 55%; the viscosity is 300 to 3000mPa.s, preferably 800 to 2000 mPa.s; the number average molecular weight is 10000-80000, preferably 30000-50000.
In another aspect of the present invention, the preparation method of the high solid content polyurethane ink resin comprises the following steps:
1) preparing a functional amine chain extender E: adding an amine chain extender and isopropanol serving as a solvent into a flask, uniformly stirring at room temperature, dropwise adding tertiary carbonic acid glycidyl ester into the mixture, finishing dropping within 0.5-1 hour, heating to 55-65 ℃, stirring and reacting for 4-6 hours to prepare a functional amine chain extender E for later use;
2) preparing a functional end-capping reagent T: putting monohydroxy tertiary amine, lactone and catalyst tetrabutyl titanate into a container, introducing nitrogen, uniformly stirring, heating to 140-160 ℃, and reacting for 24-36 hours to obtain a functional end-capping agent T for later use;
3) putting polymer polyol, polyisocyanate, a catalyst and a part of solvent into a container, introducing nitrogen, reacting at 60-120 ℃ for 3-5 hours, adding a functional end-capping agent T, continuing to react for 1-3 hours, cooling, and adding a part of solvent to obtain a prepolymer solution;
4) and (3) putting the functional amine chain extender E and the solvent into another container, uniformly stirring to obtain a chain extender solution, then dropwise adding the prepolymer solution obtained in the step 3) into the chain extender solution within 0.5-1 hour under the stirring state of a greenhouse, and then heating to 50 ℃ for reaction for 0.5-2 hours to obtain the final polyurethane ink resin.
In another aspect of the present invention, the high solid content polyurethane ink resin or the high solid content polyurethane ink resin prepared by the method is applied to solvent type gravure composite ink.
Compared with the prior art, the invention has the following beneficial effects:
the functional amine chain extender E formed by the reaction of the amine chain extender and the tertiary carbonic acid glycidyl ester has an internal plasticizing effect, so that the resin still has reduced viscosity when the resin keeps higher molecular weight; meanwhile, the functional end capping agent T formed by the reaction of monohydroxy tertiary amine and lactone enhances the affinity of the resin to the pigment and the base material by introducing flexible chain tertiary amine at the end of the resin molecule, and the synergistic effect of the two effectively overcomes the defects in the prior art, realizes the high solid content and low viscosity of the resin, and has excellent application properties such as pigment dispersibility, base material adhesion and the like.
Detailed Description
The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.
A preparation method of a high-solid-content polyurethane ink resin comprises the following steps:
1) preparing a functional amine chain extender E: adding an amine chain extender and isopropanol serving as a solvent into a flask, uniformly stirring at room temperature, dropwise adding tertiary carbonic acid glycidyl ester into the flask, finishing dropping within 0.5-1 hour, heating to 55-65 ℃, stirring and reacting for 4-6 hours to obtain a functional amine chain extender E, and keeping the functional amine chain extender E for later use.
2) Preparing a functional end-capping agent T: putting monohydroxy tertiary amine, lactone and catalyst tetrabutyl titanate into a flask, introducing nitrogen, uniformly stirring, heating to 140-160 ℃, reacting for 24-36 hours, and preparing the functional end-capping agent T for later use.
3) Putting polymer polyol, polyisocyanate, a catalyst and a part of solvent into a flask, introducing nitrogen, reacting for 3-5 hours at 60-120 ℃, adding a functional end-capping agent T, continuing to react for 1-3 hours, cooling, and adding a part of solvent to obtain a prepolymer solution.
4) And adding the functional amine chain extender E and the solvent into another flask, uniformly stirring to obtain a chain extender solution, then dropwise adding the prepolymer solution into the chain extender solution within 0.5-1 hour under the stirring state of a greenhouse, and then heating to 50 ℃ for reaction for 0.5-2 hours to obtain the final polyurethane ink resin.
The high-solid-content polyurethane ink resin is an internal-plasticization high-solid-content low-viscosity polyurethane ink resin, and the solid content of the internal-plasticization high-solid-content low-viscosity polyurethane ink resin is 40-70%, and the internal-plasticization high-solid-content low-viscosity polyurethane ink resin comprises, but is not limited to, 45%, 50%, 55%, 60%, 65% and preferably 45-55%; a viscosity of 300 to 3000mPa.s, such as but not limited to 500mPa.s, 1000mPa.s, 1200mPa.s, 1500mPa.s, 1800mPa.s, 2000mPa.s, 2500mPa.s, 3000mPa.s, preferably 800 to 2000 mPa.s; the number average molecular weight is 10000 to 80000, and includes, but is not limited to, 20000, 30000, 40000, 50000, 60000, 70000, 80000, preferably 30000 to 50000. The solid content of the polyurethane ink resin is higher than the highest value of 35% in the prior art, the solid content can be 40% -70%, the viscosity is in the range of 300-3000 mPa.s, a product with high solid content and low viscosity is really made, and the technical bias that the conventional high solid content cannot be simultaneously low in viscosity is overcome.
The high-solid-content polyurethane ink resin is prepared by reacting the following raw material components: 28-46 parts of polymer polyol, 3-15 parts of polyisocyanate, 2-9 parts of functional amine chain extender E, 0.1-13 parts of functional end-capping agent F and 30-60 parts of solvent, wherein the parts are in parts by mass.
The functional amine chain extender E is obtained by reacting an amine chain extender with tertiary carbonic acid glycidyl ester, and the reaction equation is shown as follows:
Figure BDA0003005417930000081
the reaction plays a role of internal plasticization by increasing the branching degree of the resin molecules, so that the resin still has lower viscosity when the molecular weight is larger. Wherein the molar ratio of the amine chain extender to the tertiary carboxylic acid glycidyl ester is 1: 0.1-1, and examples of the molar ratio include but are not limited to 1: 0.2, 1: 0.4, 1: 0.5, 1: 0.6, 1: 0.7, 1: 0.9, preferably 1: 0.3-0.8.
The amine chain extender refers to a compound containing at least two amine groups (primary amine or secondary amine) and capable of promoting molecular chain extension and extension, and examples thereof include, but are not limited to, at least any one of isophoronediamine, ethylenediamine, propylenediamine, 1, 6-hexamethylenediamine, 1, 4-butylenediamine, neopentyenediamine, dicyclohexylmethanediamine, 1, 4-cyclohexylenediamine, naphthylamine, sodium ethylenediamine sulfonate, sodium ethylenediamine propanesulfonate, and sodium 2, 4-diaminobenzenesulfonate; preferably, the amine chain extender is isophorone diamine or 1, 6-hexamethylene diamine.
Examples of the glycidyl versatate include, but are not limited to, at least any one of glycidyl pivalate, glycidyl neohexanoate, glycidyl neoheptanoate, glycidyl neooctanoate, glycidyl neononanoate, glycidyl neodecanoate, glycidyl neoundecanoate, and glycidyl neotridecanoate; preferably, the glycidyl versatate is glycidyl neodecanoate.
Wherein the functional end-capping reagent T is obtained by reacting monohydroxy tertiary amine with lactone, and one reaction example is represented by the following formula:
Figure BDA0003005417930000091
wherein the reaction mass ratio of the monohydroxy tertiary amine to the lactone depends on the molecular weight M of the functional end-capping reagent T of the reaction productTAnd molecular weight M of monohydroxy tertiary amineMonohydroxy tertiary aminesAs shown in the following formula:
MT＝(mlactones+mMonohydroxy tertiary amines)×MMonohydroxy tertiary amines/mMonohydroxy tertiary amines
In the formula, mLactonesIs the mass of the lactone, mMonohydroxy tertiary aminesIs the mass of the monohydroxy tertiary amine.
The function of the resin is to introduce long-chain branched amino groups at the ends of the molecules, increase the affinity of the resin molecules with pigments and base materials, further enhance the pigment dispersibility of the resin and the base material adhesion, enhance the intermolecular force of the resin to a certain extent, and counteract the side effect of reduced cohesion of the resin molecules caused by internal plasticization. The number average molecular weight of the functional end-capping agent T is 200-3000, such as but not limited to 300, 500, 800, 1000, 1500, 2000, 2500, 3000, preferably 400-2000.
Examples of the monohydroxy tertiary amine include, but are not limited to, at least any one of N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanolamine, N, N-dimethylaminopropanol, N, N-diethylaminopropanol, N, N-dipropylaminopropanol, N, N-dibutylaminopropanol, N-ethyl-N-hydroxyethylaniline, N-benzyl-N-methylethanolamine, N, N-dimethylaminoethoxyethanol; preferably, the monohydroxy tertiary amine is N, N-dimethylethanolamine or N, N-diethylethanolamine.
Examples of the lactone include, but are not limited to, at least any one of β -propiolactone, γ -butyrolactone, β -butyrolactone, δ -valerolactone, γ -valerolactone, ε -caprolactone, δ -caprolactone, γ -heptolactone, ω -octalactone, δ -octalactone, γ -octalactone, δ -nonalactone, γ -nonalactone, δ -decalactone, γ -undecalactone, δ -dodecalactone, γ -dodecalactone, δ -tetradecanolide, 15-pentadecanolide, 16-hexadecanolide, glycolide, and lactides; preferably, the lactone is any one of delta-valerolactone, gamma-valerolactone, epsilon-caprolactone, delta-caprolactone and gamma-caprolactone.
Wherein the polymer polyol refers to polyester polyol or polyether polyol, and the polyester polyol is a hydroxyl-terminated polyester compound generated by polycondensation of dihydric alcohol and dibasic acid. Examples of the dihydric alcohol include, but are not limited to, at least any one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, methylpropanediol, 1, 3-butylene glycol, 1, 4-butylene glycol, neopentyl glycol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 1, 4-cyclohexyldiol, dihydroxydiphenylsulfone, 2-bis (4-hydroxyphenyl) propane, 4' -dihydroxydiphenylmethane; examples of the dibasic acid include, but are not limited to, at least any one of sebacic acid, adipic acid, azelaic acid, terephthalic acid, isophthalic acid, phthalic acid. Preferably, the functionality of the polyester polyol is 2.
The polyether polyol means a compound obtained by polymerizing an alkylene oxide starting from a hydroxyl compound, and examples of the hydroxyl compound commonly used as an initiator include, but are not limited to, at least any one of ethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, dipropylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, hexanediol, pentanediol, 3-methyl-1, 5-pentanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 12-dodecanediol, catechol, resorcinol, bisphenol F, and bisphenol a. Examples of alkylene oxides include, but are not limited to, at least any of ethylene oxide, propylene oxide, butylene oxide. The number average molecular weight of the polymer polyol is 400 to 6000, for example, including but not limited to 800, 1500, 2000, 3000, 4000, 5000, preferably 1000 to 4000.
Examples of the polyisocyanate include, but are not limited to, at least any one of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), Naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI), 1, 4-cyclohexane diisocyanate (CHDI), Xylylene Diisocyanate (XDI), cyclohexane dimethylene diisocyanate (HXDI), trimethyl-1, 6-hexamethylene diisocyanate (TMHDI), tetramethylm-xylylene diisocyanate (TMXDI), norbornane diisocyanate (NBDI), dimethylbiphenyl diisocyanate (TODI), and methylcyclohexyl diisocyanate (HTDI). Preferably, the polyisocyanate is one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI).
In the synthesis of the isocyanate prepolymer in the step 3), a catalyst commonly used in the art may be used as the catalyst, and examples thereof include, but are not limited to, at least any one of dimethyltin diacetate, dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, dioctyltin dilaurate, zinc (II) dioctoate, zirconium acetylacetonate, 2,6, 6-tetramethyl-3, 5-heptanedionate zirconium, and bismuth 2-ethylhexanoate; dibutyltin dilaurate, bismuth neodecanoate and bismuth 2-ethylhexanoate are preferable, and bismuth neodecanoate and bismuth 2-ethylhexanoate are more preferable.
Wherein, the solvent is selected from one or more of ester, secondary alcohol and tertiary alcohol solvents; preferably one or more of ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, isopropanol, more preferably one or more of ethyl acetate, n-propyl acetate and isopropanol. It should be noted that, the specific kind of the solvent used in the step 2) and the step 3) may be the same or different, and plays a role in diluting and dissolving, and does not affect the implementation of the present invention.
The invention is further illustrated, but not limited, by the following more specific examples.
The examples and comparative examples used the following starting materials:
isophorone diisocyanate, IPDI, wanhua chemistry;
toluene diisocyanate, TDI-80, Vanhua Chemicals;
polyester polyol P1, obtained by reacting adipic acid with methyl propylene glycol, and having a number average molecular weight of 2000;
polyester polyol P2, which is obtained by the reaction of adipic acid, methyl propanediol and 1, 6-hexanediol and has a number average molecular weight of 2000;
polyester polyol P3, obtained by reacting adipic acid and 1, 2-propylene glycol, and having a number average molecular weight of 4000;
polyester polyol P4, which is obtained by the reaction of adipic acid, isophthalic acid, neopentyl glycol and diethylene glycol and has the number average molecular weight of 1000;
polyether polyol DL2000D, PPG polyether, functionality 2, number average molecular weight 2000, east Shandong Lanxingdong;
isophorone diamine, IPDA, wanhua chemistry;
1, 6-hexanediamine, HDA, wanhua chemistry;
glycidyl versatate, E10P, mezzanine;
n, N-dimethylethanolamine, DMEA, solvay;
n, N-diethylethanolamine, DEEA, alatin;
epsilon-caprolactone, bostto;
delta-valerolactone, meiji chemistry;
di-n-butylamine, DBA, alatin;
ethyl acetate, EA, jiangmen modesty chemical industry;
isopropanol, IPA, mallow petrochemical;
BICAT8118, organobismuth catalyst, U.S. advanced chemistry.
Preparation E1
50g of IPDA and 83.53g of solvent IPA are put into a flask, the mixture is uniformly stirred at room temperature, glycidyl versatate E10P 33.53.53 g is dropwise added into the mixture, the dropwise addition is finished within 0.5 hour, and then the mixture is heated to 60 ℃ and stirred for reaction for 5 hours to prepare a functional amine chain extender E1 with the molecular weight of 284.42 and the solid content of 50%.
Preparation E2
50g of HDA and 108.96g of solvent IPA are put into a flask, the mixture is stirred uniformly at room temperature, glycidyl versatate E10P 58.96.96 g is dripped into the mixture, the dripping is finished within 0.5 hour, and then the mixture is heated to 60 ℃ and stirred for reaction for 5 hours to prepare a functional amine chain extender E1 with the molecular weight of 253.22 and the solid content of 50%.
Preparation T1
10g of DMEA, 124.61g of epsilon-caprolactone and 0.01g of catalyst tetrabutyl titanate are put into a flask, nitrogen is introduced, the mixture is stirred uniformly, the temperature is raised to 140 ℃ and the mixture reacts for 24 hours, so that the functional end-capping agent T1 with the number-average molecular weight of 1200 is prepared.
Preparation T2
20g of DEEA, 116.53g of delta-valerolactone and 0.01g of catalyst tetrabutyl titanate are put into a flask, nitrogen is introduced, the mixture is uniformly stirred, the temperature is raised to 140 ℃ and the mixture reacts for 24 hours, so that the functional end-capping agent T2 with the number-average molecular weight of 800 is prepared.
The samples of the above preparation examples were bottled in sample bottles for further use.
Example Eg1
Putting 100g of polyester polyol P1, 18.99g of IPDI, 0.02g of catalyst BICAT8118 and 13g of solvent EA into a flask, introducing nitrogen, reacting at 80 ℃ for 4 hours, adding 4.27g of functional end capping agent T1, continuously reacting for 2 hours, cooling to 70 ℃, adding 54g of solvent EA, uniformly stirring, and cooling to room temperature to obtain a prepolymer solution;
in another flask, 20.25g of functional amine chain extender E1, 19.7g of solvent EA and 36.6g of solvent IPA are put into the flask and stirred uniformly to obtain a chain extender solution, then the prepolymer solution is dripped into the chain extender solution within 1 hour under the stirring state of a greenhouse, and then the temperature is raised to 50 ℃ for reaction for 1 hour to obtain polyurethane resin Eg 1.
Example Eg2
Putting 100g of polyester polyol P1, 14.76g of IPDI, 0.02g of catalyst BICAT8118 and 13g of solvent EA into a flask, introducing nitrogen, reacting for 4 hours at 80 ℃, adding 1.31g of functional end capping agent T2, continuously reacting for 2 hours, cooling to 70 ℃, adding 54g of solvent EA, stirring uniformly and cooling to room temperature to obtain a prepolymer solution;
in another flask, 8.81g of functional amine chain extender E2, 12.2g of solvent EA and 36.8g of solvent IPA are added, the mixture is stirred uniformly to obtain a chain extender solution, then the prepolymer solution is dripped into the chain extender solution within 1 hour under the stirring state of a greenhouse, and then the temperature is raised to 50 ℃ for reaction for 1 hour, so that polyurethane resin Eg2 is prepared.
Example Eg3
Putting 100g of polyester polyol P2, 18.99g of IPDI, 0.02g of catalyst BICAT8118 and 13g of solvent EA into a flask, introducing nitrogen, reacting at 80 ℃ for 4 hours, adding 2.49g of functional end capping agent T2, continuously reacting for 2 hours, cooling to 70 ℃, adding 54g of solvent EA, uniformly stirring, and cooling to room temperature to obtain a prepolymer solution;
in another flask, 20.35g of functional amine chain extender E1, 18.5g of solvent EA and 36.0g of solvent IPA are added, stirred uniformly to obtain a chain extender solution, then the prepolymer solution is dropwise added into the chain extender solution within 1 hour under the stirring state of a greenhouse, and then the temperature is raised to 50 ℃ for reaction for 1 hour, so that polyurethane resin Eg3 is prepared.
Example Eg4
Putting 100g of polyester polyol P3, 9.92g of IPDI, 0.02g of catalyst BICAT8118 and 13g of solvent EA into a flask, introducing nitrogen, reacting for 4 hours at 100 ℃, adding 2.82g of functional end capping agent T1, continuing to react for 2 hours, cooling to 70 ℃, adding 54g of solvent EA, stirring uniformly and cooling to room temperature to obtain a prepolymer solution;
in another flask, 10.23g of functional amine chain extender E2, 10.3g of solvent EA and 35.5g of solvent IPA are put into the flask and stirred uniformly to obtain a chain extender solution, then the prepolymer solution is dripped into the chain extender solution within 1 hour under the stirring state of a greenhouse, and then the temperature is raised to 50 ℃ for reaction for 1 hour to obtain the polyurethane resin Eg 4.
Example Eg5
Putting 100g of polyester polyol P4, 14.44g of IPDI, 11.31g of TDI-80, 0.02g of catalyst BICAT8118 and 13g of solvent EA into a flask, introducing nitrogen, reacting at 90 ℃ for 4 hours, adding 5.32g of functional end-capping reagent T1, continuing to react for 2 hours, cooling to 70 ℃, adding 60g of solvent EA, stirring uniformly and cooling to room temperature to obtain a prepolymer solution;
in another flask, 15.05g of functional amine chain extender E2, 17.5g of solvent EA and 40.6g of solvent IPA are added, stirred uniformly to obtain a chain extender solution, then the prepolymer solution is dropwise added into the chain extender solution within 1 hour under the stirring state of a greenhouse, and then the temperature is raised to 50 ℃ for reaction for 1 hour, so that polyurethane resin Eg5 is prepared.
Example Eg6
Putting 90g of polyester polyol P1, 10g of DL2000D, 9.42g of IPDI, 7.38g of TDI-80, 0.02g of catalyst BICAT8118 and 13g of solvent EA into a flask, introducing nitrogen, reacting for 4 hours at 90 ℃, adding 2.36g of functional end-capping agent T2, continuously reacting for 2 hours, cooling to 70 ℃, adding 54g of solvent EA, stirring uniformly and cooling to room temperature to obtain a prepolymer solution;
in another flask, 20.05g of functional amine chain extender E1, 16.3g of solvent EA and 34.8g of solvent IPA are added, stirred uniformly to obtain a chain extender solution, then the prepolymer solution is dropwise added into the chain extender solution within 1 hour under the stirring state of a greenhouse, and then the temperature is raised to 50 ℃ for reaction for 1 hour, so that polyurethane resin Eg6 is prepared.
Example Eg7
Putting 80g of polyester polyol P2, 20g of DL2000D, 18.99g of IPDI, 0.02g of catalyst BICAT8118 and 13g of solvent EA into a flask, introducing nitrogen, reacting for 4 hours at 90 ℃, adding 2.97g of functional end capping agent T1, continuously reacting for 2 hours, cooling to 70 ℃, adding 54g of solvent EA, uniformly stirring and cooling to room temperature to obtain a prepolymer solution;
in another flask, 20.55g of functional amine chain extender E1, 18.9g of solvent EA and 36.1g of solvent IPA are added, stirred uniformly to obtain a chain extender solution, then the prepolymer solution is dropwise added into the chain extender solution within 1 hour under the stirring state of a greenhouse, and then the temperature is raised to 50 ℃ for reaction for 1 hour, so that polyurethane resin Eg7 is prepared.
Example Eg8
Putting 100g of polyester polyol P1, 18.99g of IPDI, 0.02g of catalyst BICAT8118 and 13g of solvent EA into a flask, introducing nitrogen, reacting at 80 ℃ for 4 hours, adding 0.54g of functional end capping agent T1, continuously reacting for 2 hours, cooling to 70 ℃, adding 54g of solvent EA, uniformly stirring, and cooling to room temperature to obtain a prepolymer solution;
in another flask, 21.12g of functional amine chain extender E1, 59.1g of solvent EA and 58.5g of solvent IPA are put into the flask and stirred uniformly to obtain a chain extender solution, then the prepolymer solution is dripped into the chain extender solution within 1 hour under the stirring state of a greenhouse, and then the temperature is raised to 50 ℃ for reaction for 1 hour to obtain polyurethane resin Eg 8.
Example Eg9
Putting 100g of polyester polyol P1, 18.99g of IPDI, 0.02g of catalyst BICAT8118 and 13g of solvent EA into a flask, introducing nitrogen, reacting for 4 hours at 80 ℃, adding 28.22g of functional end capping agent T1, continuously reacting for 2 hours, cooling to 70 ℃, adding 25g of solvent EA, uniformly stirring, and cooling to room temperature to obtain a prepolymer solution;
in another flask, 14.77g of functional amine chain extender E1, 12.9g of solvent EA and 25g of solvent IPA are added, stirred uniformly to obtain a chain extender solution, then the prepolymer solution is dropwise added into the chain extender solution within 1 hour under the stirring state of a greenhouse, and then the temperature is raised to 50 ℃ for reaction for 1 hour, so that the polyurethane resin Eg9 is prepared.
Comparative example C1
Putting 100g of polyester polyol P1, 18.99g of IPDI, 0.02g of catalyst BICAT8118 and 13g of solvent EA into a flask, introducing nitrogen, reacting at 80 ℃ for 4 hours, cooling to 70 ℃, adding 54g of solvent EA, stirring uniformly and cooling to room temperature to obtain an isocyanate-terminated prepolymer solution;
in another flask, 6.05g of IPDA, 0.45g of DBA, 128.2 g of solvent EA and 97.6g of solvent IPA were charged and stirred to obtain a chain extender solution, and then the above isocyanate terminated prepolymer solution was added dropwise to the chain extender solution over 1 hour under stirring in a greenhouse, and then heated to 50 ℃ to react for 1 hour to obtain polyurethane resin C1.
Comparative example C2
Putting 100g of polyester polyol P1, 18.99g of IPDI, 0.02g of catalyst BICAT8118 and 13g of solvent EA into a flask, introducing nitrogen, reacting at 80 ℃ for 4 hours, cooling to 70 ℃, adding 54g of solvent EA, stirring uniformly and cooling to room temperature to obtain an isocyanate-terminated prepolymer solution;
in another flask, 6.05g of IPDA, 0.45g of DBA, 16.7g of solvent EA and 41.8g of solvent IPA were charged and stirred to obtain a chain extender solution, and then the above isocyanate terminated prepolymer solution was added dropwise to the chain extender solution over 1 hour under stirring in a greenhouse, and then heated to 50 ℃ to react for 1 hour to obtain polyurethane resin C2.
Comparative example C3
Putting 100g of polyester polyol P1, 18.99g of IPDI, 0.02g of catalyst BICAT8118 and 13g of solvent EA into a flask, introducing nitrogen, reacting at 80 ℃ for 4 hours, cooling to 70 ℃, adding 54g of solvent EA, stirring uniformly and cooling to room temperature to obtain an isocyanate-terminated prepolymer solution;
in another flask, 4.28g of IPDA, 3.15g of DBA, 17.3g of solvent EA and 42.1g of solvent IPA were charged and stirred to obtain a chain extender solution, and then the above isocyanate terminated prepolymer solution was added dropwise to the chain extender solution over 1 hour under stirring in a greenhouse, and then heated to 50 ℃ to react for 1 hour to obtain polyurethane resin C3.
Comparative example C4
Putting 100g of polyester polyol P1, 18.99g of IPDI, 0.02g of catalyst BICAT8118 and 13g of solvent EA into a flask, introducing nitrogen, reacting at 80 ℃ for 4 hours, cooling to 70 ℃, adding 54g of solvent EA, stirring uniformly and cooling to room temperature to obtain an isocyanate-terminated prepolymer solution;
in another flask, 20.25g of functional amine chain extender E1, 0.46g of DBA, 18.4g of solvent EA and 34.1g of solvent IPA were put into the flask and stirred uniformly to obtain a chain extender solution, then the above isocyanate terminated prepolymer solution was added dropwise to the chain extender solution over 1 hour under stirring in a greenhouse, and then the temperature was raised to 50 ℃ to react for 1 hour to obtain polyurethane resin C4.
Comparative example C5
Putting 100g of polyester polyol P1, 18.99g of IPDI, 0.02g of catalyst BICAT8118 and 13g of solvent EA into a flask, introducing nitrogen, reacting for 4 hours at 80 ℃, adding 4.27g of functional end capping agent T1, continuously reacting for 2 hours, cooling to 70 ℃, adding 54g of solvent EA, uniformly stirring, and cooling to room temperature to obtain a prepolymer solution;
in another flask, 6.06g of IPDA, 25.7g of solvent EA and 36.6g of solvent IPA were charged, and stirred uniformly to obtain a chain extender solution, then the above prepolymer solution was added dropwise to the chain extender solution over 1 hour under stirring in a greenhouse, and then heated to 50 ℃ to react for 1 hour, to obtain polyurethane resin C5.
The resin indexes obtained in the above examples and comparative examples are summarized in Table 1.
TABLE 1 characteristics and indices of resins of examples and comparative examples
Figure BDA0003005417930000191
The polyurethane resins obtained in the examples and comparative examples were prepared as inks: according to the formula shown in the table 2, the raw materials are filled into a 500ml iron can, glass beads with the same mass and the diameter of 1mm are added, after sealing, the raw materials are ground for 3-4 hours by a paint quick mixer, and the polyurethane ink for gravure printing is obtained. The parts are parts by mass.
TABLE 2 formulation of ester-soluble polyurethane gravure inks
Raw materials White ink PR146 Red ink PR15:4 blue ink
Polyurethane resin 24 24 24
Pigment (I) 32 12 13
Vinyl chloride-vinyl acetate copolymer 2 2.8 3
Dispersant 24000 0.1 0.2 0.2
Wax powder 3620 0.1 0.2 0.2
Matting powder 820A 0.3 0.4 0.4
N-propyl acetate 40 46.4 43.2
Isopropanol (I-propanol) 3.5 6 6
Propylene glycol methyl ether -- 3 3
Acetic acid n-butyl ester -- 5 7
Total of 100 100 100
The inks prepared were tested as follows:
(1) ink gloss test
The test method comprises the following steps: reference is made to GB/T13217.2-2009.
Evaluation criteria: excellent represents good gloss; o represents a normal gloss; x represents a gloss difference.
(2) Ink tinting strength test
The test method and the evaluation standard refer to GB/T13217.6-2008. The tinting strength test standard was selected, among others, for the ink prepared for the formulation of example Eg 1.
(3) Ink leveling test
The test method comprises the following steps: the polyester film (PET) was subjected to ink printing using a KPP gravure ink proofing machine (150 lines/inch by RK, UK, a hierarchical plate), the ink film was dried with a blower, the state of the coated surface was observed, and the leveling property of the ink was evaluated.
Evaluation criteria: very good indicates that the leveling is good and the ink layer is uniform and has no spots; o indicates that leveling is normal, the ink layer is relatively uniform with a few spots; the x indicates a poor leveling, an uneven ink layer or a large number of spots.
(4) Ink resolubility test
The test method comprises the following steps: printing ink proofing is carried out by using a KPP gravure printing ink proofing machine (manufactured by RK company in British, 150 lines/inch of a printing plate), after the printing ink on the printing plate is dried, about 1-2 g of testing solvent is taken by a dropper to be quickly dripped on an ink layer of the printing plate, and then timing is carried out; after 30 seconds, the solvent was blown off by a blower to expose the ink layer and the printing plate covered with the solvent, and the state of dissolution of the ink layer was observed.
Evaluation criteria: very good means that the ink layer is obviously dissolved and the printing plate is cleaner; o indicates that the ink layer is partially dissolved and the plate is not clean; x indicates that the ink layer is clearly insoluble.
(5) Ink adhesion fastness test
The test method comprises the following steps: reference is made to GB/T13217.7-2009.
Evaluation criteria: excellent indicates that the adhesive force is good and the ink layer does not drop completely; o indicates that the adhesion was normal and the ink layer was peeled off a small portion; the x indicates the difference in adhesion and the ink layer was mostly peeled off.
(6) Ink anti-blocking test
The test method comprises the following steps: reference is made to GB/T13217.8-2009.
Evaluation criteria: excellent indicates no blocking; o indicates light blocking; x represents severe blocking.
The test results are shown in tables 3 to 5, respectively.
TABLE 3 gravure polyurethane white ink test results
Item Eg1 Eg2 Eg3 Eg4 Eg5 Eg6 Eg7 Eg8 Eg9 C1 C3 C4
Gloss of ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ × ○
Coloring power 100 101 103 98 103 98 95 90 110 60 × 88
Leveling property ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ × ○
Redissolving property ◎ ◎ ◎ ◎ ○ ◎ ◎ ○ ◎ ○ ◎ ○
Adhesion of PET ◎ ◎ ◎ ○ ◎ ○ ○ ○ ◎ ○ × ○
Adhesion of BOPP ○ ○ ○ ○ ◎ ○ ○ ○ ◎ × × ×
Anti-adhesion ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ × ◎ × ◎
Table 4 gravure polyurethane red ink test results
Item Eg1 Eg2 Eg3 Eg4 Eg5 Eg6 Eg7 Eg8 Eg9 C1 C3 C4
Gloss of ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ ○ × ○
Coloring power 100 103 104 97 102 98 95 90 110 68 × 85
Leveling property ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ × ○
Redissolution property ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ ○ ◎ ○
Adhesion of PET ◎ ◎ ◎ ○ ○ ○ ○ ○ ◎ ○ × ○
Adhesion of BOPP ○ ○ ○ ○ ○ ○ ○ × ◎ × × ×
Anti-adhesion ◎ ○ ◎ ◎ ◎ ◎ ◎ ◎ × ◎ × ◎
TABLE 5 gravure polyurethane blue ink test results
Item Eg1 Eg2 Eg3 Eg4 Eg5 Eg6 Eg7 Eg8 Eg9 C1 C3 C4
Gloss of ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ ○ × ○
Coloring power 100 101 104 99 102 98 96 90 110 67 × 84
Leveling property ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ × ○
Redissolving property ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ ○ ◎ ○
Adhesion of PET ◎ ◎ ◎ ○ ○ ◎ ○ ○ ◎ ○ × ○
Adhesion of BOPP ○ ○ ○ ○ ○ ○ ○ × ◎ × × ×
Anti-adhesion ◎ ○ ◎ ○ ◎ ◎ ◎ ◎ × ◎ × ◎
The test results of examples and comparative examples were analyzed. As can be seen from the comparison of the resin indexes of the examples and comparative examples in Table 1, if the molecular weight of the resin with 30% solid content prepared in the conventional manner is kept unchanged, and the solid content is increased to 50%, the viscosity of the resin is so large that the resin loses fluidity that the resin cannot be used for preparing the ink. If the viscosity is reduced by means of molecular weight reduction, the inks prepared therewith do not meet the practical requirements in terms of pigment dispersion, adhesion and blocking resistance, see comparative example C3 in tables 3 to 5. In tables 3-5, using examples Eg1-Eg7 made according to the present invention, the overall ink performance was significantly improved compared to comparative example C1, which was made in a conventional manner at 30% solids. Examples Eg8 and Eg9 are extreme examples of molecular weight or solids index prepared using the present invention to show the breadth of coverage of the process, but some of the examples have slightly poorer performance properties than the preferred range since the index is not in the preferred range, but all of the properties are better than the comparative examples. Comparative example C4 was prepared using functional chain extender E but not using functional end-capping reagent T, and although the resin could also achieve high solids content and low viscosity, the ink prepared therewith was not sufficient in pigment dispersion and substrate adhesion, comparative example C5 used only functional end-capping reagent T but not functional chain extender E, and the resin could not achieve high solids content and low viscosity, and could not be used to prepare ink at 50% solids content because of excessive viscosity.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications and adaptations to the invention may be made in light of the teachings of the present disclosure. Such modifications or adaptations are intended to be within the scope of the present invention as defined by the claims.

Claims (29)

1. The high-solid-content polyurethane ink resin is characterized by being prepared by reacting the following raw materials in parts by mass: 28-46 parts of polymer polyol, 3-15 parts of polyisocyanate, 2-9 parts of functional amine chain extender E, 0.1-13 parts of functional end capping agent T and 30-60 parts of solvent;
the functional amine chain extender E is formed by reacting an amine chain extender with tertiary carbonic acid glycidyl ester;
the functional end-capping reagent T is prepared by reacting monohydroxy tertiary amine with lactone;
the amine chain extender is selected from primary amine or secondary amine containing at least two amine groups;
the monohydroxy tertiary amine is selected from monohydroxy tertiary amines with one end being a hydroxyl group and the other end being a tertiary amine.
2. The high-solid-content polyurethane ink resin according to claim 1, wherein the molar ratio of the amine chain extender to the glycidyl versatate is 1: 0.1-1.
3. The high-solid content polyurethane ink resin according to claim 2, wherein the molar ratio of the amine chain extender to the glycidyl versatate is 1: 0.3-0.8.
4. The high solid content polyurethane ink resin according to claim 1, wherein the amine chain extender is at least one selected from the group consisting of isophoronediamine, ethylenediamine, propylenediamine, 1, 6-hexamethylenediamine, 1, 4-butylenediamine, neopentyldiamine, dicyclohexylmethanediamine, 1, 4-cyclohexenediamine, naphthylamine, sodium ethylenediamine ethanesulfonate, sodium ethylenediamine propanesulfonate, and sodium 2, 4-diaminobenzenesulfonate.
5. The high solid content polyurethane ink resin of claim 4, wherein the amine chain extender is selected from isophorone diamine or 1, 6-hexamethylene diamine.
6. The high-solid content polyurethane ink resin according to claim 1, wherein the glycidyl versatate is at least one selected from the group consisting of glycidyl pivalate, glycidyl neohexanoate, glycidyl neoheptanoate, glycidyl neooctanoate, glycidyl neononanoate, glycidyl neodecanoate, glycidyl neoundecanoate, and glycidyl neotridecanoate.
7. The high solid content polyurethane ink resin of claim 6, wherein the glycidyl versatate is glycidyl neodecanoate.
8. The high-solid content polyurethane ink resin according to claim 1, wherein the number average molecular weight of the functional end-capping agent T is 200 to 3000.
9. The high-solid content polyurethane ink resin according to claim 8, wherein the number average molecular weight of the functional blocking agent T is 400 to 2000.
10. The high-solids polyurethane ink resin according to claim 1, wherein the tertiary monohydroxy amine is at least any one selected from the group consisting of N, N-dimethylethanolamine, N-diethylethanolamine, N-dipropylethanolamine, N-dibutylethanolamine, N-dimethylaminopropanol, N-diethylaminopropanol, N-dipropylaminopropanol, N-dibutylaminopropanol, N-ethyl-N-hydroxyethylaniline, N-benzyl-N-methylethanolamine, N-dimethylaminoethoxyethanol.
11. The high solids polyurethane-containing ink resin of claim 10, wherein the tertiary monohydroxy amine is N, N-dimethylethanolamine or N, N-diethylethanolamine.
12. The high-solid content polyurethane ink resin according to claim 1, wherein the lactone is an aliphatic cyclic lactone.
13. The high solids polyurethane ink resin of claim 12, wherein the lactone is selected from at least any one of β -propiolactone, γ -butyrolactone, β -butyrolactone, δ -valerolactone, γ -valerolactone, ε -caprolactone, δ -caprolactone, γ -heptalactone, ω -octalactone, δ -octalactone, γ -octalactone, δ -nonalactone, γ -nonalactone, δ -decalactone, γ -undecalactone, δ -dodecalactone, γ -dodecalactone, δ -tetradecanolide, 15-pentadecanolide, 16-hexadecanolide, glycolide, and lactide.
14. The high-solid content polyurethane ink resin according to claim 13, wherein the lactone is at least any one selected from the group consisting of δ -valerolactone, γ -valerolactone, e-caprolactone, δ -caprolactone and γ -caprolactone.
15. The high-solid content polyurethane ink resin according to claim 1, wherein the polymer polyol is selected from polyester polyol or polyether polyol.
16. The high solid content polyurethane ink resin of claim 15, wherein the polymer polyol has a functionality of 2 to 3 and a number average molecular weight of 400 to 6000.
17. The high-solid content polyurethane ink resin according to claim 16, wherein the polymer polyol has a functionality of 2 and a number average molecular weight of 1000 to 4000.
18. The high solid content polyurethane ink resin of claim 15, wherein the polyester polyol is a hydroxyl terminated polyester polyol formed by polycondensation of a diol and a diacid; the dihydric alcohol is at least one selected from ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, methyl propylene glycol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 1, 4-cyclohexyl diol, dihydroxy diphenyl sulfone, 2-bis (4-hydroxyphenyl) propane and 4, 4' -dihydroxy diphenyl methane; the dibasic acid is at least one selected from sebacic acid, adipic acid, azelaic acid, terephthalic acid, isophthalic acid and phthalic acid.
19. The high solid content polyurethane ink resin of claim 15, wherein the polyether polyol is selected from the group consisting of polyether polyols obtained by polymerizing alkylene oxides with a hydroxyl compound as an initiator.
20. The high solids content polyurethane ink resin of claim 19, wherein the hydroxyl compound as an initiator is selected from at least any one of propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, hexanediol, pentanediol, 3-methyl-1, 5-pentanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 12-dodecanediol, catechol, resorcinol, bisphenol F, bisphenol a; the alkylene oxide is at least any one selected from ethylene oxide, propylene oxide and butylene oxide.
21. The high-solid content polyurethane ink resin according to claim 1, wherein the polyisocyanate is at least any one selected from Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), 1, 4-cyclohexane diisocyanate (CHDI), cyclohexane dimethylene diisocyanate (HXDI), trimethyl-1, 6-hexamethylene diisocyanate (TMHDI), and methylcyclohexyl diisocyanate (HTDI).
22. The high-solid content polyurethane ink resin according to claim 21, wherein the polyisocyanate is at least any one selected from Toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI).
23. The high-solid content polyurethane ink resin as claimed in claim 1, wherein the solvent is selected from one or more of ester, secondary alcohol and tertiary alcohol.
24. The high solids polyurethane ink resin of claim 23, wherein the solvent is selected from one or more of ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, and isopropyl alcohol.
25. The high solids content polyurethane ink resin of claim 24, wherein the solvent is selected from one or more of ethyl acetate, n-propyl acetate, and isopropyl alcohol.
26. The high solid content polyurethane ink resin of any one of claims 1 to 25, wherein the solid content of the polyurethane ink resin is 40% to 70%; the viscosity is 300-3000 mPa.s; the number average molecular weight is 10000-80000.
27. The high solids content polyurethane ink resin of claim 26, wherein the polyurethane ink resin has a solids content of 45% to 55%; the viscosity is 800-2000 mPa.s; the number average molecular weight is 30000-50000.
28. The method for preparing the high solid content polyurethane ink resin as claimed in any one of claims 1 to 27, comprising the steps of:
1) preparing a functional amine chain extender E: adding an amine chain extender and isopropanol serving as a solvent into a flask, uniformly stirring at room temperature, dropwise adding tertiary carbonic acid glycidyl ester into the mixture, finishing dropping within 0.5-1 hour, heating to 55-65 ℃, stirring and reacting for 4-6 hours to prepare a functional amine chain extender E for later use;
2) preparing a functional end-capping reagent T: putting monohydroxy tertiary amine, lactone and catalyst tetrabutyl titanate into a container, introducing nitrogen, uniformly stirring, heating to 140-160 ℃, and reacting for 24-36 hours to obtain a functional end-capping agent T for later use;
3) putting polymer polyol, polyisocyanate, a catalyst and a part of solvent into a container, introducing nitrogen, reacting at 60-120 ℃ for 3-5 hours, adding a functional end-capping agent T, continuing to react for 1-3 hours, cooling, and adding a part of solvent to obtain a prepolymer solution;
4) and (3) adding the functional amine chain extender E and the solvent into another container, uniformly stirring to obtain a chain extender solution, then dropwise adding the prepolymer solution obtained in the step 3) into the chain extender solution within 0.5-1 hour under the condition of stirring at room temperature, and then heating to 50 ℃ for reaction for 0.5-2 hours to obtain the final polyurethane ink resin.
29. Use of the high solid content polyurethane ink resin of any one of claims 1 to 27 or the high solid content polyurethane ink resin prepared by the method of claim 28 in a solvent-based gravure ink set.
CN202110360669.1A 2021-04-02 2021-04-02 High-solid-content polyurethane ink resin, preparation method and application thereof Active CN113122122B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110360669.1A CN113122122B (en) 2021-04-02 2021-04-02 High-solid-content polyurethane ink resin, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110360669.1A CN113122122B (en) 2021-04-02 2021-04-02 High-solid-content polyurethane ink resin, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113122122A CN113122122A (en) 2021-07-16
CN113122122B true CN113122122B (en) 2022-07-12

Family

ID=76774722

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110360669.1A Active CN113122122B (en) 2021-04-02 2021-04-02 High-solid-content polyurethane ink resin, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113122122B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114933845B (en) * 2022-05-07 2023-05-26 浙江鑫柔科技有限公司 Thermosetting weather-proof protective coating material and preparation method and application thereof
CN115403725B (en) * 2022-08-15 2023-12-15 黄山中泽新材料有限公司 Polyurethane binder for high-solid low-viscosity ink, and preparation method and device thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007112936A (en) * 2005-10-21 2007-05-10 Asahi Kasei Chemicals Corp Highly crosslinkable high solid urethane coating composition
CN105622886A (en) * 2014-11-18 2016-06-01 万华化学（北京）有限公司 Alcohol/water-soluble polyurethane resin used for intaglio ink and preparation method thereof
CN108859350A (en) * 2018-05-21 2018-11-23 浙江西溪玻璃有限公司 A kind of shock resistance organic glass and its preparation process
CN110862336A (en) * 2019-10-29 2020-03-06 中国科学院山西煤炭化学研究所 Alcohol amine chain extender, preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007112936A (en) * 2005-10-21 2007-05-10 Asahi Kasei Chemicals Corp Highly crosslinkable high solid urethane coating composition
CN105622886A (en) * 2014-11-18 2016-06-01 万华化学（北京）有限公司 Alcohol/water-soluble polyurethane resin used for intaglio ink and preparation method thereof
CN108859350A (en) * 2018-05-21 2018-11-23 浙江西溪玻璃有限公司 A kind of shock resistance organic glass and its preparation process
CN110862336A (en) * 2019-10-29 2020-03-06 中国科学院山西煤炭化学研究所 Alcohol amine chain extender, preparation method and application

Also Published As

Publication number Publication date
CN113122122A (en) 2021-07-16

Similar Documents

Publication Publication Date Title
CN113122122B (en) High-solid-content polyurethane ink resin, preparation method and application thereof
CN110791246B (en) Adhesive composition and method
CN102089342B (en) Aqueous polyurethane resin dispersion, manufacturing method for same, and paint composition containing same
RU2473570C2 (en) Acidified polyester polyurethyane dispersions
US11802204B2 (en) Thermoset omniphobic compositions with improved barrier properties, related articles, and related methods
CN101173032A (en) Large-molecular weight polyurethane acrylic ester and synthesizing method thereof
US20120276296A1 (en) Water-based coating compositions
US20100197857A1 (en) Polyurethane for printing ink binders, method for producing the same and printing ink
CN110483728B (en) Preparation method of strippable waterborne polyurethane resin and application of strippable waterborne polyurethane resin in coating
TW200940582A (en) Wetting agents and dispersants, their preparation and use
US20150353771A1 (en) Coating compositions with an aqueous dispersion containing a polyurethane and an acid reactive crosslinking agent
CN110498900B (en) Polyurethane resin for high black color-developing leather and preparation method thereof
JP2019112583A (en) Ink set and decorative material
CZ2001417A3 (en) Aqueous sealing layer based on polyurethane dispersions
CN110818881B (en) Preparation method of polyurethane ink resin, polyurethane ink resin prepared by preparation method and ink
EP0646609A1 (en) Aqueous dispersion of an aqueous, hydrazine-terminated polyurethane
US3267058A (en) Polyurethanes prepared from polyisocyanates and polyols derived from hydroxyl copolymers
US20230159694A1 (en) Waterborne epoxy resin for anti-corrosion coating, and preparation method and use thereof
JP2014196413A (en) Resin composition for photogravure printing ink
US9834702B2 (en) Jet-black multilayer coating film and forming method thereof
CN111087571A (en) Solvent-resistant diluted polyurethane ink binder and preparation method and application thereof
CN114057980B (en) Self-dispersible ester-soluble polyurethane ink resin, preparation method and ink
KR101990796B1 (en) Composition of solvent-based gravure ink using polyalkylene carbonate and manufacturing method for thereof
JP2002226755A (en) Printing ink composition
CN112341589B (en) Polyurethane resin for high color fastness and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant