Modified rosin resin for UV (ultraviolet) ink as well as preparation method and application of modified rosin resin
By synergistically reacting modified silicone oil with rosin resin, a modified rosin resin with excellent flexibility and weather resistance was prepared, which solved the problems of brittleness and insufficient weather resistance of rosin resin in existing UV offset printing inks and improved the performance of UV inks.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHAOGUAN DERUI CHEM IND CO LTD
- Filing Date
- 2026-03-11
- Publication Date
- 2026-05-12
AI Technical Summary
Existing modified rosin resins for UV offset printing inks suffer from problems such as high softening point, high hardness, poor flexibility, and poor weather resistance, which affect their application in some fields.
Modified silicone oil was prepared by chain extension reaction of hydroxyl silicone oil with epoxy silane monomers and silane monomers containing unsaturated double bonds. It was then reacted with disproportionated rosin resin, epoxy resin and trimellitic anhydride curing agent to form modified rosin resin, introducing unsaturated double bonds to participate in the photocuring reaction of UV inks.
It significantly improves the flexibility, gloss and weather resistance of modified rosin resin, while maintaining good adhesion and enhancing the performance of UV inks.
Abstract
Description
Technical Field
[0001] This invention belongs to the field of modified polymer materials technology, specifically relating to a modified rosin resin for UV inks, its preparation method, and its application. Background Technology
[0002] Modified rosin resins are widely used in offset printing inks due to their excellent pigment wetting properties, good film-forming and adhesion properties, and ability to impart suitable viscoelasticity and rheological properties to binders. Modified rosin resins directly affect the gloss, drying properties, water resistance, tack, rheological properties, and printability of printing inks. Currently, the modified rosin resins used in UV offset printing inks are mainly rosin-modified phenolic resins, which are polymeric products generated through the chemical reaction of alkylphenols (currently used phenols in offset printing inks include phenol, PTBP p-tert-butylphenol, POP p-tert-octylphenol, PNP nonylphenol, and PDDP dodecylphenol), formaldehyde, polyols, and rosin. However, in practical applications, rosin-modified phenolic resins still have the following problems: 1. High softening point (generally above 150℃), high hardness, overall brittleness and poor flexibility; 2. High esterification reaction temperature of alkylphenols or polyols with rosin, producing water, resulting in a darker color of the modified product, with the color (Fe-Co) difficult to reach below 12#; 3. Poor weather resistance, with poor gloss retention under humid heat and sunlight aging conditions. These problems limit its application in some fields. Summary of the Invention
[0003] In view of the shortcomings and deficiencies of the existing technology, the primary objective of this invention is to provide a method for preparing modified rosin resin for UV inks.
[0004] Another object of the present invention is to provide a modified rosin resin prepared by the above method.
[0005] Another object of the present invention is to provide the application of the above-mentioned modified rosin resin in UV inks.
[0006] The objective of this invention is achieved through the following technical solution:
[0007] A method for preparing a modified rosin resin for UV inks includes the following preparation steps:
[0008] (1) Hydroxyl silicone oil is subjected to chain extension reaction with epoxy silane monomer and silane monomer containing unsaturated double bonds under the condition of silanol catalyst to obtain modified silicone oil containing epoxy group and unsaturated double bond;
[0009] (2) Disproportionated rosin resin and catalyst are added to solvent to dissolve and mix. The mixture is heated to 80~120℃ under a protective atmosphere. Then, modified silicone oil containing epoxy groups and unsaturated double bonds, epoxy resin, and trimellitic anhydride curing agent are added for heat preservation reaction. After the reaction is completed, the solvent is removed by vacuum distillation to obtain modified rosin resin.
[0010] Preferably, the hydroxyl silicone oil is a low-viscosity hydroxyl silicone oil with a viscosity of 20-200 cSt at 25°C. The aforementioned low-viscosity hydroxyl silicone oil has a molecular weight in the range of approximately 500-6000 g / mol and exhibits high chain extension reactivity.
[0011] Preferably, the epoxy silane monomer is selected as 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane (KH-563) or 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane (KH-564).
[0012] Preferably, the silane monomer containing unsaturated double bonds is methyl vinyl dimethoxysilane (YS-2171), methyl vinyl diethoxysilane (YS-2172), methacryloyloxypropyl methyl dimethoxysilane, or methacryloyloxypropyl methyl diethoxysilane.
[0013] Preferably, the mass ratio of the hydroxyl silicone oil to the epoxy silane monomer and the silane monomer containing unsaturated double bonds is 100:1~10:1~10.
[0014] Preferably, the silanolate catalyst is sodium silanolate or potassium silanolate.
[0015] Preferably, the chain extension reaction is carried out at a temperature of 100-120°C for 2-8 hours.
[0016] This invention prepares a polysiloxane containing both epoxy groups and unsaturated double bonds through a dealcoholization condensation chain extension reaction of hydroxyl silicone oil with epoxy silane monomers and silane monomers containing unsaturated double bonds. The epoxy groups can react with the carboxyl groups in disproportionated rosin resin and further undergo a curing and crosslinking reaction with epoxy resin and trimellitic anhydride curing agent, thereby achieving chemical modification of the disproportionated rosin resin. The introduced unsaturated double bonds can participate in the photocuring reaction of UV inks, thereby improving the performance of UV inks.
[0017] Preferably, the catalyst in step (2) is triethylamine, N / N dimethylaniline, N / N dimethylbenzylamine, triphenylphosphine, benzyltrimethylammonium chloride, tetramethylammonium chloride or tetrabutylammonium bromide.
[0018] Preferably, the solvent is one or more of cyclohexanone, ethyl acetate, dimethylformamide, and methyl ethyl ketone.
[0019] Preferably, the epoxy resin is a bisphenol A type epoxy resin or a bisphenol F type epoxy resin.
[0020] Preferably, the mass ratio of the disproportionated rosin resin to the modified silicone oil containing epoxy groups and unsaturated double bonds, epoxy resin, and trimellitic anhydride curing agent is 100:5~20:50~100:15~30.
[0021] The modified rosin resin of this invention improves adhesion by reacting with epoxy resin, enhances flexibility and weather resistance by reacting with modified silicone oil, introduces unsaturated double bonds capable of photocuring with UV inks, and improves the reactivity and compatibility of each component by reacting with trimellitic anhydride curing agent. The synergistic effect of these components enhances the modification effect.
[0022] Further preferred, the reaction order of each material in step (2) is as follows: first add modified silicone oil containing epoxy groups and unsaturated double bonds and keep it warm for 1~3h, then add epoxy resin and keep it warm for 1~3h, and finally add trimellitic anhydride curing agent and keep it warm for 2~4h.
[0023] The principle behind the above reaction sequence is as follows: First, modified silicone oil containing epoxy groups and unsaturated double bonds is added for reaction. The disproportionated rosin resin forms chemical bonds with the epoxy groups and / or hydroxyl groups of the modified silicone oil through carboxyl groups. Then, epoxy resin is added for reaction, forming chemical bonds with the remaining carboxyl groups in the disproportionated rosin resin. Finally, trimellitic anhydride curing agent is added to cure and crosslink with the remaining epoxy groups. This reaction sequence can improve the directional bonding effect between the poorly compatible modified silicone oil and the disproportionated rosin resin, thereby improving the compatibility and modification effect of each component.
[0024] A modified rosin resin for UV inks is prepared by the above method.
[0025] The application of the above-mentioned modified rosin resin in UV inks.
[0026] Compared with the prior art, the beneficial effects of the present invention are:
[0027] (1) The present invention uses specific silicone oil components to modify disproportionated rosin resin, which can significantly improve its flexibility, gloss and weather resistance.
[0028] (2) The present invention uses epoxy resin to modify disproportionated rosin resin, which can avoid the defect of reduced adhesion due to the introduction of silicone oil components and ensure good adhesion. Detailed Implementation
[0029] The present invention will be further described in detail below with reference to embodiments, but the implementation of the present invention is not limited thereto.
[0030] Example 1
[0031] (1) Hydroxyl silicone oil (viscosity 75 cSt, average molecular weight 3200 g / mol) was added to a reaction vessel with epoxy silane monomer KH-564 and silane monomer YS-2171 containing unsaturated double bonds in a mass ratio of 100:5:5. After stirring and mixing, the mixture was heated to 110°C, and then potassium trimethylsilanolate catalyst was added for a heat preservation chain extension reaction for 5 h. Low-boiling substances were removed under reduced pressure to obtain modified silicone oil containing epoxy groups and unsaturated double bonds. The viscosity of the product was measured to be 2000 cSt, the average molecular weight was 35500 g / mol, the epoxy group content was 0.89 wt%, and the vinyl group content was 0.96 wt%.
[0032] (2) 100 parts by mass of disproportionated rosin resin and 0.2 parts of NN dimethylaniline catalyst were added to 250 parts of cyclohexanone solvent to dissolve and mix. The mixture was heated to 100°C under nitrogen protection. 12 parts of modified silicone oil containing epoxy groups and unsaturated double bonds were added and the reaction was kept at the temperature for 2 hours. The epoxy value of the product was measured to confirm the completion of the reaction. Then 68 parts of bisphenol A epoxy resin (E-51) were added and the reaction was kept at the temperature for 2 hours. The acid value of the product (mgKOH / g) was measured to be ≤10. Then 20 parts of trimellitic anhydride curing agent were added and the reaction was kept at the temperature for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation to obtain modified rosin resin.
[0033] The modified rosin resin obtained in this embodiment has a softening point of 115℃, an acid value (mgKOH / g) ≤10, and a color (Fe-Co) ≤10#.
[0034] Example 2
[0035] (1) Hydroxyl silicone oil (viscosity 100 cSt, average molecular weight 4000 g / mol) was added to a reaction vessel with epoxy silane monomer KH-564 and silane monomer YS-2171 containing unsaturated double bonds in a mass ratio of 100:7:3. After stirring and mixing, the mixture was heated to 110°C, and then potassium trimethylsilanolate catalyst was added for a heat preservation chain extension reaction for 5 h. Low-boiling substances were removed under reduced pressure to obtain modified silicone oil containing epoxy groups and unsaturated double bonds. The viscosity of the product was measured to be 3000 cSt, the average molecular weight was 41600 g / mol, the epoxy group content was 1.15 wt%, and the vinyl group content was 0.55 wt%.
[0036] (2) 100 parts by mass of disproportionated rosin resin and 0.2 parts of NN dimethylaniline catalyst were added to 250 parts of cyclohexanone solvent to dissolve and mix. The mixture was heated to 100°C under nitrogen protection. 15 parts of modified silicone oil containing epoxy groups and unsaturated double bonds were added and the reaction was kept at the temperature for 2 hours. The epoxy value of the product was measured to confirm the completion of the reaction. Then 70 parts of bisphenol A epoxy resin (E-51) were added and the reaction was kept at the temperature for 2 hours. The acid value of the product (mgKOH / g) was measured to be ≤10. Then 25 parts of trimellitic anhydride curing agent were added and the reaction was kept at the temperature for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation to obtain modified rosin resin.
[0037] The modified rosin resin obtained in this embodiment has a softening point of 118℃, an acid value (mgKOH / g) ≤10, and a color (Fe-Co) ≤10#.
[0038] Example 3
[0039] (1) Hydroxyl silicone oil (viscosity 150 cSt, average molecular weight 5100 g / mol) was added to a reaction vessel with epoxy silane monomer KH-564 and silane monomer YS-2171 containing unsaturated double bonds in a mass ratio of 100:4:6. After stirring and mixing, the mixture was heated to 110 °C, and then potassium trimethylsilanolate catalyst was added for a heat preservation chain extension reaction for 6 h. Low-boiling substances were removed under reduced pressure to obtain modified silicone oil containing epoxy groups and unsaturated double bonds. The viscosity of the product was measured to be 4000 cSt, the average molecular weight was 48500 g / mol, the epoxy group content was 0.70 wt%, and the vinyl group content was 1.12 wt%.
[0040] (2) 100 parts by mass of disproportionated rosin resin and 0.2 parts of NN dimethylaniline catalyst were added to 250 parts of cyclohexanone solvent to dissolve and mix. The mixture was heated to 100°C under nitrogen protection. 20 parts of modified silicone oil containing epoxy groups and unsaturated double bonds were added and the reaction was kept at the temperature for 3 hours. The epoxy value of the product was measured to confirm the completion of the reaction. Then 80 parts of bisphenol A epoxy resin (E-51) were added and the reaction was kept at the temperature for 2 hours. The acid value of the product (mgKOH / g) was measured to be ≤10. Then 25 parts of trimellitic anhydride curing agent were added and the reaction was kept at the temperature for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation to obtain modified rosin resin.
[0041] The modified rosin resin obtained in this embodiment has a softening point of 111℃, an acid value (mgKOH / g) ≤10, and a color (Fe-Co) ≤10#.
[0042] Example 4
[0043] (1) Hydroxyl silicone oil (viscosity 50 cSt, average molecular weight 2500 g / mol) was added to a reaction vessel with epoxy silane monomer KH-564 and silane monomer YS-2171 containing unsaturated double bonds in a mass ratio of 100:7:7. After stirring and mixing, the mixture was heated to 110°C, and then potassium trimethylsilanolate catalyst was added for a heat preservation chain extension reaction for 6 h. Low-boiling substances were removed under reduced pressure to obtain modified silicone oil containing epoxy groups and unsaturated double bonds. The viscosity of the product was measured to be 1800 cSt, the average molecular weight was 30400 g / mol, the epoxy group content was 1.17 wt%, and the vinyl group content was 1.26 wt%.
[0044] (2) 100 parts by mass of disproportionated rosin resin and 0.2 parts of NN dimethylaniline catalyst were added to 250 parts of cyclohexanone solvent to dissolve and mix. The mixture was heated to 100°C under nitrogen protection. 5 parts of modified silicone oil containing epoxy groups and unsaturated double bonds were added and the reaction was kept at the temperature for 3 hours. The epoxy value of the product was measured to confirm the completion of the reaction. Then 50 parts of bisphenol A epoxy resin (E-51) were added and the reaction was kept at the temperature for 2 hours. The acid value of the product (mgKOH / g) was measured to be ≤10. Then 15 parts of trimellitic anhydride curing agent were added and the reaction was kept at the temperature for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation to obtain modified rosin resin.
[0045] The modified rosin resin obtained in this embodiment has a softening point of 120℃, an acid value (mgKOH / g) ≤10, and a color (Fe-Co) ≤10#.
[0046] Example 5
[0047] (1) The preparation method of the modified silicone oil containing epoxy groups and unsaturated double bonds is the same as that in Example 1.
[0048] (2) 100 parts by mass of disproportionated rosin resin, 0.2 parts of NN dimethylaniline catalyst, 12 parts of modified silicone oil containing epoxy groups and unsaturated double bonds, and 68 parts of bisphenol A epoxy resin (E-51) were added to 250 parts of cyclohexanone solvent to dissolve and mix. The mixture was heated to 100°C under nitrogen protection and kept at the temperature for 4 hours. The acid value of the product (mgKOH / g) was measured to be ≤10. Then, 20 parts of trimellitic anhydride curing agent were added and the mixture was kept at the temperature for 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation to obtain modified rosin resin.
[0049] The modified rosin resin obtained in this embodiment has a softening point of 117℃, an acid value (mgKOH / g) ≤10, and a color (Fe-Co) ≤10#.
[0050] Comparative Example 1
[0051] Compared to Example 1, this comparative example did not involve the addition of modified silicone oil during the reaction. The specific steps are as follows:
[0052] 100 parts by weight of disproportionated rosin resin and 0.2 parts by weight of NN dimethylaniline catalyst were added to 250 parts by weight of cyclohexanone solvent and dissolved and mixed. The mixture was heated to 100°C under nitrogen protection, and 68 parts by weight of bisphenol A epoxy resin (E-51) were added and the reaction was maintained at this temperature for 2 hours. The acid value of the product (mgKOH / g) was measured and found to be ≤10. Then, 20 parts by weight of trimellitic anhydride curing agent were added and the reaction was maintained at this temperature for another 3 hours. After the reaction was completed, the solvent was removed by vacuum distillation to obtain modified rosin resin.
[0053] The modified rosin resin obtained in this comparative example has a softening point of 148℃, an acid value (mgKOH / g) ≤10, and a color (Fe-Co) ≤10#.
[0054] Comparative Example 2
[0055] Compared to Example 1, this comparative example does not involve the addition of epoxy resin and curing agent during the reaction. The specific steps are as follows:
[0056] (1) The preparation method of the modified silicone oil containing epoxy groups and unsaturated double bonds is the same as that in Example 1.
[0057] (2) 100 parts by mass of disproportionated rosin resin and 0.2 parts of N,N dimethylaniline catalyst were added to 250 parts of cyclohexanone solvent to dissolve and mix. The mixture was heated to 100°C under nitrogen protection. 12 parts of modified silicone oil containing epoxy groups and unsaturated double bonds were added and the reaction was kept at the temperature for 2 hours. The epoxy value of the product was measured to confirm the completion of the reaction. The solvent was removed by vacuum distillation to obtain the modified rosin resin.
[0058] The modified rosin resin obtained in this comparative example has a softening point of 91℃ and a color (Fe-Co) ≤10#.
[0059] A comparison of the results with those of Comparative Examples 1-2 and Example 1 shows that the addition of modified silicone oil to modify rosin resin can significantly reduce the softening point of the resulting modified rosin resin, while the reaction between epoxy resin and curing agent can increase the softening point of the resulting modified rosin resin.
[0060] The modified rosin resins obtained in the above examples and comparative examples were tested for performance in UV inks, and the application formulations are as follows:
[0061] 50 parts acrylate monomer, 30 parts modified rosin resin, 15 parts pigments and fillers, 5 parts photoinitiator, and 0.2 parts polymerization inhibitor.
[0062] Curing process: Curing is performed by UV-LED lamps with a wavelength of 320~400nm, and the substrate is PET.
[0063] The test results for the adhesion (GB / T9286-2021), flexibility (bending 200 times at 90℃ and observing whether the paint film cracks), gloss (spectrophotometer test) and weather resistance (gloss retention rate after 40 days of accelerated aging treatment in a xenon lamp aging chamber at 85℃ and 85% humidity) of the corresponding products are shown in Table 1 below.
[0064] Table 1. Application performance results of modified rosin resins in Examples 1-5 and Comparative Examples 1-2
[0065] sample Adhesion flexibility gloss Weather resistance Example 1 Level 0 No cracks 65° 89.2% Example 2 Level 0 No cracks 67° 91.0% Example 3 Level 0 No cracks 68° 88.2% Example 4 Level 0 No cracks 61° 91.8% Example 5 Level 1 No cracks 63° 82.5% Comparative Example 1 Level 0 Obvious cracks 50° 72.0% Comparative Example 2 Level 2 No cracks 62° 87.1%
[0066] As shown in Table 1, the modification of disproportionated rosin resin using specific silicone oil components in this invention significantly improves its flexibility, gloss, and weather resistance. Furthermore, the synergistic modification through epoxy resin curing and crosslinking avoids the reduced adhesion caused by the introduction of silicone oil components, ensuring good adhesion. Additionally, a comparison between Example 5 and Example 1 shows that the modification effect of this invention, which involves reacting the disproportionated rosin resin with a modified silicone oil containing epoxy groups and unsaturated double bonds, is better, further improving adhesion and weather resistance.
[0067] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.
Claims
1. A method for preparing a modified rosin resin for UV inks, characterized in that: The preparation steps include the following: (1) Hydroxyl silicone oil is subjected to chain extension reaction with epoxy silane monomer and silane monomer containing unsaturated double bonds under the condition of silanol catalyst to obtain modified silicone oil containing epoxy group and unsaturated double bond; (2) Disproportionated rosin resin and catalyst are added to solvent to dissolve and mix. The mixture is heated to 80~120℃ under a protective atmosphere. Then, modified silicone oil containing epoxy groups and unsaturated double bonds, epoxy resin, and trimellitic anhydride curing agent are added for heat preservation reaction. After the reaction is completed, the solvent is removed by vacuum distillation to obtain modified rosin resin.
2. The method for preparing a modified rosin resin for UV inks according to claim 1, characterized in that: The hydroxyl silicone oil is selected as a low-viscosity hydroxyl silicone oil with a viscosity of 20~200 cSt at 25℃; the epoxy silane monomer is selected as 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane or 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane; the silane monomer containing unsaturated double bonds is methyl vinyldimethoxysilane, methyl vinyldiethoxysilane, methacryloxypropylmethyldimethoxysilane or methacryloxypropylmethyldiethoxysilane.
3. The method for preparing a modified rosin resin for UV inks according to claim 2, characterized in that: The mass ratio of the hydroxyl silicone oil to the epoxy silane monomer and the silane monomer containing unsaturated double bonds is 100:1~10:1~10.
4. The method for preparing a modified rosin resin for UV inks according to claim 1, characterized in that: The silanolate catalyst is sodium silanolate or potassium silanolate; the chain extension reaction temperature is 100~120℃, and the reaction time is 2~8h.
5. The method for preparing a modified rosin resin for UV inks according to claim 1, characterized in that: The catalyst mentioned in step (2) is triethylamine, N / N dimethylaniline, N / N dimethylbenzylamine, triphenylphosphine, benzyltrimethylammonium chloride, tetramethylammonium chloride or tetrabutylammonium bromide; the solvent is one or more of cyclohexanone, ethyl acetate, dimethylformamide and methyl ethyl ketone.
6. The method for preparing a modified rosin resin for UV inks according to claim 1, characterized in that: The epoxy resin is either bisphenol A type epoxy resin or bisphenol F type epoxy resin.
7. The method for preparing a modified rosin resin for UV inks according to claim 1, characterized in that: The mass ratio of the disproportionated rosin resin to the modified silicone oil containing epoxy groups and unsaturated double bonds, epoxy resin, and trimellitic anhydride curing agent is 100:5~20:50~100:15~30.
8. The method for preparing a modified rosin resin for UV inks according to claim 1, characterized in that: The reaction order of each material in step (2) is as follows: first, add modified silicone oil containing epoxy groups and unsaturated double bonds and keep it warm for 1-3 hours; then add epoxy resin and keep it warm for 1-3 hours; finally, add trimellitic anhydride curing agent and keep it warm for 2-4 hours.
9. A modified rosin resin for UV inks prepared by the preparation method according to any one of claims 1 to 8.
10. The application of the modified rosin resin according to claim 9 in UV inks.