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CN-122011836-A - Degradable environment-friendly aging-resistant UV (ultraviolet) ink and preparation method thereof

CN122011836ACN 122011836 ACN122011836 ACN 122011836ACN-122011836-A

Abstract

The invention belongs to the technical field of UV (ultraviolet) curing ink and discloses degradable environment-friendly aging-resistant UV ink and a preparation method thereof. The printing ink mainly comprises 2, 5-furandicarboxylic acid-itaconic acid block hyperbranched polyester acrylate resin, 1, 4-cyclohexanedimethanol diacrylate, tetrahydrofuranacrylate, 4-hydroxybenzophenone grafted polycaprolactone monoacrylate photoinitiator, a colorant and an auxiliary agent. The invention realizes the cooperative promotion of the ink performance through the working procedures of the synthesis of the matched resin and the photoinitiator, the pigment grafting pretreatment, the gradient low-temperature prepolymerization and the like, the obtained ink is biodegradable under the composting condition, and has excellent ageing resistance, no migration risk of the photoinitiator, good storage stability and printability, and can be widely applied to the printing scenes with high requirements on environmental protection and use stability, such as food contact package, environmental protection labels and the like.

Inventors

  • LIU ZONGLIN
  • YU CAIYUN

Assignees

  • 中山市炫丽新材料技术有限公司

Dates

Publication Date
20260512
Application Date
20260320

Claims (10)

  1. 1. The degradable environment-friendly aging-resistant UV ink is characterized by comprising the following components in parts by weight, 45-65 Parts of 2, 5-furandicarboxylic acid-itaconic acid block hyperbranched polyester acrylate resin; 8-15 parts of 1, 4-cyclohexanedimethanol diacrylate; 7-15 parts of tetrahydrofuran acrylic ester; 3-8 parts of a 4-hydroxybenzophenone grafted polycaprolactone monoacrylate photoinitiator; 5-18 parts of a colorant; 0.2-1 part of polyether modified polydimethylsiloxane flatting agent; 0.3-1.5 parts of polyethylene wax dispersing agent; 0.1-0.5 part of antioxidant.
  2. 2. The degradable environment-friendly aging-resistant UV ink of claim 1, wherein the colorant is any one of rutile titanium dioxide, phthalocyanine blue BGS or carbon black N330.
  3. 3. The degradable environment-friendly aging-resistant UV ink of claim 1, wherein the polyether-modified polydimethylsiloxane leveling agent is BYK-333.
  4. 4. The degradable environment-friendly aging-resistant UV ink of claim 1, wherein the polyethylene wax dispersing agent is BYK-9076.
  5. 5. The degradable environment-friendly aging-resistant UV ink of claim 1, wherein the antioxidant is antioxidant 1010.
  6. 6. A preparation method of degradable environment-friendly aging-resistant UV ink is characterized by comprising the following steps of, S1, adding 1, 4-butanediol and itaconic acid into a reaction kettle, starting stirring, controlling the stirring rotation speed to be 200-400r/min, adding 2, 5-furandicarboxylic acid, p-toluenesulfonic acid and hydroquinone, replacing nitrogen for 2-4 times, protecting nitrogen in the whole process, heating to 145-150 ℃ for preserving heat and pre-dispersing for 30min, heating to 160-170 ℃ for reacting for 2.5-3.5h, continuously separating water generated by the reaction by a condensation reflux device until the acid value of the system is reduced to 25-30mgKOH/g, maintaining 160-170 ℃ for carrying out decompression polycondensation for 25-35min at the vacuum degree of minus 0.095-0.1 MPa, obtaining carboxyl end linear block polyester prepolymer, cooling the prepolymer to 130 ℃, supplementing hydroquinone, continuously cooling to 115-125 ℃, adding pentaerythritol triacrylate, preserving heat in the whole process, controlling the stirring rotation speed to be 150-300r/min, preserving heat for 2.5-3.5h until the acid value of the system is reduced to below 5mgKOH/g, stopping the reaction, maintaining 115-125 mgKOH/g, distilling at the vacuum degree of minus 0.095-0.5 MPa for carrying out decompression for 25-35min, and obtaining the end carboxyl end linear block polyester prepolymer, and cooling the end carboxyl block polyester resin by distilling at the vacuum degree of minus 0.095-55-35 ℃ to obtain the end carboxyl block polyester resin; S2, adding the dried 4-hydroxybenzophenone and epsilon-caprolactone into a reaction kettle, replacing nitrogen for 2-4 times, protecting by nitrogen in the whole process, starting stirring, controlling the stirring rotation speed to be 250-400r/min, heating to 130-135 ℃ and preserving heat for 30min until the 4-hydroxybenzophenone is completely melted, adding stannous octoate, preserving heat for 125-135 ℃ and reacting for 4.5-5.5h, reducing the system hydroxyl value to be 55-65mgKOH/g, maintaining 125-135 ℃ and distilling under reduced pressure for 25-35min at the vacuum degree of minus 0.095 to minus 0.1MPa to obtain a hydroxyl-terminated polycaprolactone grafted 4-hydroxybenzophenone intermediate, cooling the intermediate to 85-95 ℃, adding acrylic acid, p-toluenesulfonic acid and hydroquinone, replacing nitrogen for 2-4 times, continuously separating water generated by a condensation reflux device, controlling the stirring rotation speed to be 200-350r/min, heating to 105-115 ℃ and preserving heat for 2.5-3.5h until the system hydroxyl value is reduced to below 8mgKOH/g, stopping reacting, maintaining 105-115 ℃ and distilling under reduced pressure for 0.5-35 MPa to obtain the hydroxyl-terminated polycaprolactone grafted 4-hydroxy-5 MPa, and distilling under reduced pressure at the vacuum degree of minus 0.0.0 to 45-35 ℃ to obtain the single-hydroxyl-terminated benzophenone; S3, adding the colorant, 10-15 parts of the resin prepared in the step S1 and the polyethylene wax dispersing agent into a reaction kettle, replacing nitrogen for 2-4 times, heating to 75-85 ℃ under the protection of nitrogen in the whole process, stirring for 30min at a rotating speed of 1000-1200r/min for pre-dispersing, and then stirring for 1-2h at a rotating speed of 800-1000r/min for heat preservation to obtain the pigment grafting pre-dispersion; S4, adding the rest resin prepared in the step S1, 4-cyclohexanedimethanol diacrylate, tetrahydrofuran acrylate, the photoinitiator prepared in the step S2, a polyether modified polydimethylsiloxane flatting agent and an antioxidant into the pigment grafting pre-dispersion prepared in the step S3, controlling the temperature to 35-40 ℃, stirring at the rotating speed of 1400-1600r/min for 10min for premixing, keeping the temperature and the rotating speed unchanged, and synchronously carrying out intermittent irradiation by adopting UV-LED light with the wavelength of 365nm and the power density of 0.3-0.5W/cm < 2 >, so as to obtain a pre-polymerization mixed system; S5, introducing the prepolymerization mixed system prepared in the step S4 into a horizontal sand mill, wherein the grinding medium is zirconia beads with the thickness of 0.3-0.5mm, the grinding temperature is controlled below 35 ℃, and the grinding is carried out until the fineness of the system is less than or equal to 5 mu m, so as to obtain an abrasive; S6, introducing the abrasive prepared in the step S5 into a high-pressure homogenizer, controlling the homogenizing temperature to be less than or equal to 35 ℃, circularly homogenizing for 2 times under the pressure of 60-80MPa, then transferring into a vacuum defoaming kettle for defoaming, and discharging to obtain the degradable environment-friendly aging-resistant UV ink.
  7. 7. The method for preparing the degradable environment-friendly aging-resistant UV ink according to claim 6, wherein in the step S1, 32-40 parts by weight of 1, 4-butanediol, 32-45 parts by weight of itaconic acid, 30-32 parts by weight of 2, 5-furandicarboxylic acid, 0.2-0.3 part by weight of p-toluenesulfonic acid, 0.05-0.10 part by weight of initial hydroquinone, 0.10-0.15 part by weight of supplemental hydroquinone and 18-22 parts by weight of pentaerythritol triacrylate are calculated.
  8. 8. The method for preparing the degradable environment-friendly aging-resistant UV ink according to claim 6, wherein in the step S2, 18-22 parts by weight of 4-hydroxybenzophenone, 55-80 parts by weight of epsilon-caprolactone, 0.08-0.20 part by weight of stannous octoate, 7-9 parts by weight of acrylic acid, 0.15-0.25 part by weight of p-toluenesulfonic acid and 0.08-0.12 part by weight of hydroquinone are calculated.
  9. 9. The method for preparing the degradable environment-friendly aging-resistant UV ink according to claim 6, wherein intermittent irradiation in the step S4 is paused for 18-22S every irradiation for 8-12S, and the accumulated time length of the actual lighting irradiation of the UV-LED lamp is 48-72S.
  10. 10. The method for preparing the degradable environment-friendly aging-resistant UV ink according to claim 6, wherein the defoaming in the step S6 is carried out at the speed of 250-350r/min for 15-25min under the conditions of the vacuum degree of minus 0.095 to minus 0.1MPa and the temperature of 30-35 ℃.

Description

Degradable environment-friendly aging-resistant UV (ultraviolet) ink and preparation method thereof Technical Field The invention belongs to the technical field of UV (ultraviolet) curing ink, and particularly relates to degradable environment-friendly aging-resistant UV ink and a preparation method thereof. Background The UV curing ink has been widely used in a plurality of fields such as package printing, label printing, paper decoration and the like by virtue of the characteristics of no emission of volatile organic compounds, high curing speed and low production energy consumption. Along with the continuous upgrading of the storage and control requirements of the whole ball ring, the requirements of the biodegradability, migration safety and long-term use stability of the printing ink are more stringent in subdivision scenes such as food contact packaging, degradable flexible packaging and the like. In the prior art, aliphatic polyester resin is used as a film forming matrix in most of the related degradable UV ink, although biodegradation to a certain degree can be realized, the core performance contradiction generally exists that ester bonds of a polyester main chain are easy to break due to ultraviolet irradiation, so that the aging resistance of an ink curing film is insufficient, the stability in the using stage and the degradability after discarding are difficult to be considered, and a small molecular photoinitiator matched with the conventional ink is easy to migrate and separate out, has potential safety hazards of food contact and cannot form a synergistic degradation effect with the degradable matrix. The prior art adopts a conventional mixed-ground ink preparation process, the problems of uneven dispersion, aggregation and sedimentation in storage period of pigment in a degradable polyester matrix are easy to occur, and meanwhile, the shrinkage rate of the ink after solidification is high and the adhesion force of a base material is insufficient. At present, a stable technical scheme capable of simultaneously achieving high biodegradability, excellent ageing resistance, low migration risk and good printability is not formed in the industry, and the rapid development requirement of the environment-friendly packaging industry is difficult to be matched. Disclosure of Invention In order to overcome the defects in the prior art, the embodiment of the invention provides degradable environment-friendly aging-resistant UV ink and a preparation method thereof, and solves the problems that the degradable UV ink in the prior art is difficult to consider both biodegradability and aging resistance, the migration risk of a photoinitiator is high, and pigment dispersion stability and printability are insufficient. In order to solve the problems, the invention provides the following technical scheme: the degradable environment-friendly aging-resistant UV ink comprises the following components in parts by weight, 45-65 Parts of 2, 5-furandicarboxylic acid-itaconic acid block hyperbranched polyester acrylate resin; 8-15 parts of 1, 4-cyclohexanedimethanol diacrylate; 7-15 parts of tetrahydrofuran acrylic ester; 3-8 parts of a 4-hydroxybenzophenone grafted polycaprolactone monoacrylate photoinitiator; 5-18 parts of a colorant; 0.2-1 part of polyether modified polydimethylsiloxane flatting agent; 0.3-1.5 parts of polyethylene wax dispersing agent; 0.1-0.5 part of antioxidant. Further, the colorant is any one of rutile titanium dioxide, phthalocyanine blue BGS or carbon black N330. The selected pigment has no difficult degradation group, has good compatibility with the degradable resin system, resists ultraviolet irradiation and meets the aging resistance requirement of the system. Further, the polyether modified polydimethylsiloxane leveling agent is BYK-333. The leveling agent can reduce the surface tension of the ink system, improve the spreadability of the ink on a substrate, and does not influence the curing and degradation performances of the system. Further, the polyethylene wax dispersing agent is BYK-9076. The dispersing agent can anchor the surfaces of pigment particles, reduce the aggregation risk of the pigment and improve the dispersion stability of the pigment in a degradable resin system. Further, the antioxidant is antioxidant 1010. The antioxidant can capture the active free radical of the system, inhibit the curing of the ink and the thermal oxidation aging in use, and improve the weather resistance of the system. The degradable environment-friendly aging-resistant UV ink disclosed by the invention takes 2, 5-furandicarboxylic acid-itaconic acid block hyperbranched polyester acrylate resin as a film forming main body, and 1, 4-cyclohexanedimethanol diacrylate and tetrahydrofuranacrylate are matched as active diluents, and 4-hydroxybenzophenone grafted polycaprolactone monoacrylate photoinitiator is adopted to match the curing requirement of a system, and a colorant, a flatting agent, a dispers