Modified rosin phenolic resin, preparation method thereof and offset printing frosted ink

Abstract

The invention relates to the technical field of novel resin and application thereof, in particular to modified rosin phenolic resin, a preparation method thereof and offset printing frosted ink. The modified rosin phenolic resin comprises silica powder grafted rosin phenolic resin, and the preparation method of the modified rosin phenolic resin comprises the following steps: preparing the silica powder grafted rosin resin, and modifying the phenolic resin by the silica powder grafted rosin resin. The resin is used for offset printing frosted ink, enables the frosted ink to be uniformly and stably transferred to the surface of a printing stock, is good in transfer property, uniform in frosted effect and good in concave-convex feeling, effectively enhances the adhesive force of a base material, is suitable for high-speed offset printing, and is excellent in printing adaptability.

Description

Technical Field

[0001] The present application belongs to the technical field of novel resins and their application, and specifically relates to a modified rosin phenolic resin and a preparation method thereof and offset frosted ink. Background Art

[0002] Matte ink is widely used because of its specific sandy properties. After printing matte ink, the product surface shows a good visual effect. With the development of society, existing customers are no longer satisfied with the visual matte feeling, and have also put forward requirements for the touch of matte ink.

[0003] Ink that has a frosted feel both visually and tactilely has high requirements for printing materials. However, in the current printing process, especially in large-scale industrial production, there are inevitably problems such as poor sand feeling, whitening on the surface of printed products, ink failure, and poor adhesion of printed products, which cannot meet the increasing commercial printing requirements. Therefore, it is urgent to find a frosted ink with a frosted feel, which has good transfer performance, good transferability, long non-skinning time on the machine, and low heavy metal content in the ink product. The main film-forming resin of offset frosted ink is rosin phenolic resin. When the current rosin phenolic resin is used as frosted ink, excessive addition of frosted powder results in poor ink transferability and weak adhesion. Summary of the invention

[0004] In view of the problems of poor transferability and weak adhesion to substrates of existing frosted inks, the present application provides a modified rosin phenolic resin and a preparation method thereof and offset frosted ink.

[0005] In the first aspect, the present application provides a modified rosin phenolic resin, which adopts the following technical solution: A modified rosin phenolic resin comprises silicon micropowder grafted rosin phenolic resin. The preparation method comprises: preparing silicon micropowder grafted rosin resin, and then modifying the silicon micropowder grafted rosin resin to modify the phenolic resin.

[0006] By modifying the unique honeycomb structure of rosin phenolic resin, the offset ink film has good adhesion, fluidity, color development and gloss. By grafting silicon micropowder on the rosin resin, the dispersion of silicon micropowder in the resin and the offset stability are increased, and the uniform stability of the ink is improved. Small particles are formed on the surface of the offset ink, showing a matte effect. The silicon micropowder is evenly dispersed in the ink layer, the matte effect is good, and the amount of matte powder is reduced. The ink has good transferability during printing, fast fixation speed after printing, good transferability, and can also improve friction resistance and light resistance; the printing effect of the printed product is bright and bright, forming a uniform matte surface, with a strong three-dimensional sense and good surface effect.

[0007] The preparation steps of the silicon powder grafted rosin phenolic resin include: (1) adding a catalyst and formaldehyde to an alkylphenol, stirring, and reacting at 100-110° C. for 2-5 hours to obtain a resol phenolic resin; (2) adding rosin to polyol, adding a catalyst, and carrying out an esterification reaction at 180-220° C. for 6-9 hours to obtain rosin ester, adding modified silicon micropowder and methyl acrylate under nitrogen protection, maintaining the temperature at 100-120° C., and then dripping an initiator. After the dripping is completed, the reaction is continued for 1-3 hours, and the modified rosin ester is obtained by distillation under reduced pressure; (3) maintaining the system temperature at 200-220° C., slowly stirring and dropping the resol phenolic resin of step (1) into the modified rosin ester of step (2), continuing the reaction for 1-2 hours, and performing vacuum distillation to obtain a silicon micropowder-grafted rosin phenolic resin.

[0008] Preferably, the mass ratio of the rosin ester to the modified silica powder is 1:(0.3-1.8).

[0009] Preferably, the modified silicon micropowder is silicon micropowder modified by a silane coupling agent containing unsaturated double bonds.

[0010] Under the action of a catalyst, formaldehyde forms a resol phenolic resin containing a large amount of active hydroxymethyl in an alkylphenol solution, and more condensates of phenol structural units can be synthesized; by using a certain range of proportions of rosin ester and modified silicon micropowder, the grafting rate of the modified rosin phenolic resin silicon micropowder is increased and the dispersibility of the modified silicon micropowder is increased. The present application creatively modifies the rosin ester with a silane coupling agent, and the modified rosin ester reacts with the resol phenolic resin to obtain a silicon micropowder grafted rosin phenolic resin with a relatively stable structure and composition.

[0011] The modified rosin phenolic resin also includes polyketone resin and epoxy soybean oil modified acrylic resin.

[0012] By adding polyketone resin and epoxy soybean oil modified acrylic resin to modified rosin phenolic resin and using them in combination with silicon micropowder grafted rosin phenolic resin, the frosted ink is evenly transferred during offset printing, presenting a uniform and stable matte effect; silicon micropowder grafted rosin phenolic resin allows silicon micropowder to be well dispersed, allowing silicon micropowder to be transferred to the surface of the substrate through the printing press; with the help of the unique honeycomb structure characteristics of silicon micropowder grafted rosin phenolic resin, the wetting properties of solid substances such as silicon micropowder are improved, so that the frosted ink has good adhesion, fluidity, color development and frosted surface stability, and reduces the surface tension of offset printing; adding polyketone resin can improve the high temperature resistance, weather resistance and yellowing resistance of the frosted ink on the one hand, and on the other hand, it can improve the frosted ink with silicon micropowder grafted rosin Phenolic resin has good compatibility, and together they improve the wettability and dispersibility of silica powder in matte ink, making it have the characteristics of high gloss, high adhesion, high hardness, etc. On this basis, epoxy soybean oil is added to modify acrylic resin, and vegetable oil modification makes the compatibility of acrylate and silica powder grafted rosin phenolic resin better, thereby enhancing the uniform dispersion of modified rosin phenolic resin, and further improving the toughness and viscosity of modified rosin phenolic resin by introducing epoxy. The prepared offset ink has fast fixing and drying speed, good transferability, high gloss, enhanced adhesion to the substrate, suitable for high-speed offset printing, and excellent printing adaptability; it prevents the toughness of matte ink materials from decreasing, and is prone to local deinking, curling, poor transferability and transferability during the offset printing process, thereby affecting the quality and efficiency of offset printing.

[0013] The preparation method of the epoxy soybean oil modified acrylic resin comprises the following steps: taking hydroxyethyl acrylate and maleic anhydride as raw materials, mixing, adding triethylamine, stirring and reacting at 95-110° C. for 1-2 hours, adding phthalic anhydride and continuing the reaction for 1-1.5 hours, adding epoxy soybean oil, cooling the system to 60-75° C., adding hydroxyethyl methacrylate and diisocyanate, stirring and reacting for 3-5 hours, and obtaining the epoxy soybean oil modified acrylic resin.

[0014] The molar ratio of the hydroxyethyl methacrylate to the diisocyanate is (0.8-1.5):1.

[0015] Any method for preparing epoxy soybean oil modified acrylic resin can be used for the preparation of the modified acrylic resin of the present application. The present application selects the above conventional modification process: a large number of hydroxyl groups are obtained by reacting hydroxyethyl acrylate and acid anhydride, and reacted with diisocyanate under the condition of adding epoxy soybean oil. The polymerization reaction is completed by a certain molar ratio of hydroxyethyl methacrylate and diisocyanate to obtain epoxy soybean oil modified acrylic resin, which is beneficial to improve the adhesion of the system.

[0016] In the second aspect, the present application provides a method for preparing a modified rosin phenolic resin, adopting the following technical scheme: a method for preparing a modified rosin phenolic resin, comprising the following steps: comprising the following steps: adding silicon micropowder grafted rosin phenolic resin, polyketone resin and epoxy soybean oil modified acrylic resin to palm oil, with a rotation speed of 200-300r / min and stirring for 20-30min to obtain a modified rosin phenolic resin.

[0017] In a third aspect, the present application provides an offset frosted ink, which adopts the following technical solution: An offset frosting ink comprises 60-80wt% of modified rosin phenolic resin.

[0018] The offset frosted ink further comprises the following components in percentages: 1-5wt% of frosted powder, 1-3wt% of adhesion promoter, 1-4wt% of superdispersant, 0.8-5wt% of carbon black, and the remainder is auxiliary agent.

[0019] By adopting the above technical scheme, the silicon micropowder grafted rosin phenolic resin, polyketone resin and epoxy soybean oil modified acrylic resin are used in combination, so that frosting powder, super dispersant, carbon black, additives and other substances are more stably dispersed in the modified rosin phenolic resin, which is beneficial to the uniform transfer of frosting ink during offset printing; the silicon micropowder grafted rosin phenolic resin and frosting powder are used in combination, so that an excellent frosting effect can be achieved even when the frosting powder content in the ink is small, and the frosting powder is transferred to the surface of the substrate through a printing press, further enhancing the offset frosting feeling of the frosting ink, enhancing the adhesion of the substrate, being suitable for high-speed offset printing, and having excellent printing adaptability.

[0020] Preferably, the frosting powder is polytetrafluoroethylene powder.

[0021] Preferably, the auxiliary agent is a leveling agent and a defoaming agent in a mass ratio of (1-3):1.

[0022] In summary, this application has the following beneficial effects: 1. Through the modification of rosin resin by silicon micropowder grafting, the dispersion performance of silicon micropowder in the resin and the offset printing stability are increased, the uniform stability of the ink is improved, and a small granular ink film is formed on the surface of the offset ink, showing a matte effect, reducing the amount of matte powder, good transferability during printing, fast fixing speed, and improved friction resistance and light resistance; making the printing effect of the printed matter bright and vivid, forming a uniform matte surface, strong three-dimensional sense, and good surface effect.

[0023] 2. By adding polyketone resin, epoxy soybean oil modified acrylic resin and silicon micropowder grafted rosin phenolic resin to the modified rosin phenolic resin, the frosted ink is evenly transferred during offset printing, presenting a uniform and stable matte effect; silicon micropowder grafted rosin phenolic resin allows silicon micropowder to be well dispersed, and the prepared frosted ink has good adhesion, fluidity, color development and frosted surface stability. Polyketone resin is added to improve the high temperature resistance, weather resistance and yellowing resistance of the frosted ink. Epoxy soybean oil modified acrylic resin is added, and vegetable oil modification makes the compatibility of acrylate and silicon micropowder grafted rosin phenolic resin better, thereby strengthening the uniform dispersion of the modified rosin phenolic resin, and further improving the toughness and viscosity of the modified rosin phenolic resin. The prepared offset printing ink has fast fixing and drying speed, good transferability, high gloss, enhanced adhesion to the substrate, is suitable for high-speed offset printing, and has excellent printing adaptability.

[0024] 3. Formaldehyde forms a resol phenolic resin containing a large amount of active methylol in a solution of alkylphenol, which can synthesize condensates of more phenol structural units; by using a certain range of proportions of rosin ester and modified silica powder, the grafting rate of the modified rosin phenolic resin silica powder is increased and the dispersibility of the modified silica powder is improved. The present application creatively modifies the rosin ester with a silane coupling agent, and the modified rosin ester reacts with the resol phenolic resin to obtain a silica powder-grafted rosin phenolic resin with a relatively stable structure and composition. DETAILED DESCRIPTION

[0025] The present application is further described in detail below in conjunction with embodiments.

[0026] raw material Some of the raw materials used in the preparation examples and embodiments: rosin-modified phenolic resin is DCH2103 rosin-modified phenolic resin; polyketone resin model: HBX-120B; super dispersant is dispersant S-17000; leveling agent is; TEGO GlideB1484; defoaming agent is BYK-052; epoxidized soybean oil: Wuhan Jixin Yibang Biotechnology Co., Ltd.; acrylate was purchased from Hebei Kailian Biotechnology Co., Ltd., and the adhesion promoter is HU290; silicon micropowder product number: S299106; polytetrafluoroethylene micropowder brand SGW-140.

[0027] The raw materials used in the examples and comparative examples that are not otherwise specified are all conventional products that can be purchased from the market.

[0028] Preparation Example Preparation example of epoxy soybean oil modified acrylic resin Preparation Example 1 Take 52g of hydroxyethyl acrylate and 27g of maleic anhydride as raw materials, mix them, add 0.4g of triethylamine, stir and react at 100°C for 1h, add 22g of phthalic anhydride and continue to react for 1h, then add 55g of epoxy soybean oil, cool the system to 75°C, add hydroxyethyl acrylate and isophorone diisocyanate, stir and react for 3h to obtain epoxy soybean oil modified acrylic resin, wherein the total amount of hydroxyethyl acrylate and isophorone diisocyanate is 10g, and the molar ratio is 0.8:1.

[0029] Modified rosin phenolic resin Preparation Example 2 0.7 g of octadecylamine and 73 g of solid formaldehyde with a concentration of 96% were added to 200 g of dodecylphenol, stirred, and reacted at 110° C. for 2 h to obtain a resol phenolic resin; (2) 452 g of horsetail rosin was added to 48 g of pentaerythritol, and 1.2 g of zinc oxide was added, and an esterification reaction was carried out at 220° C. for 6 h to obtain rosin ester; Add 63 g of γ-methacryloxypropyltrimethoxysilane to 250 g of 45% ethanol solution, then add 150 g of silicon micropowder, heat at 100° C., stir and reflux for 3 h, filter and dry at 60° C. to obtain modified silicon micropowder; Under nitrogen protection, 57g of rosin ester, 17.1g of modified silica powder and 46g of methyl acrylate were added, the temperature was kept at 110°C, and 1.8g of azobisisobutyronitrile was added dropwise. After the addition was completed, the reaction was continued for 3h, and the low-boiling fraction was removed by vacuum distillation to obtain modified rosin ester; (3) Keeping the system temperature at 220° C., taking 110 g of the resol phenolic resin of step (1) and slowly stirring and dropping it into the modified rosin ester of step (2), continuing the reaction for 1 hour, removing the low boiling point fraction by vacuum distillation to obtain a silicon micropowder grafted rosin phenolic resin, adding it into palm oil with 1 / 5 times the volume of the silicon micropowder grafted rosin phenolic resin, rotating at 300 r / min, stirring for 30 minutes, and obtaining a modified rosin phenolic resin.

[0030] Preparation Example 3 (1) 0.7 g of octadecylamine and 73 g of solid formaldehyde with a concentration of 96% were added to 200 g of dodecylphenol, and the mixture was stirred and reacted at 110° C. for 2 h to obtain a resol phenolic resin; (2) 452 g of horsetail rosin was added to 48 g of pentaerythritol, and 1.2 g of zinc oxide was added, and an esterification reaction was carried out at 220° C. for 6 h to obtain rosin ester; Add 63 g of γ-methacryloxypropyltrimethoxysilane to 250 g of 45% ethanol solution, then add 150 g of silicon micropowder, heat at 100° C., stir and reflux for 3 h, filter and dry at 60° C. to obtain modified silicon micropowder; Under nitrogen protection, 57g of rosin ester, 10.4g of modified silicon powder and 46g of methyl acrylate were added, the temperature was kept at 110°C, and 1.8g of azobisisobutyronitrile was added dropwise. After the addition was completed, the reaction was continued for 3h, and the low-boiling fraction was removed by vacuum distillation to obtain modified rosin ester; (3) Keeping the system temperature at 220° C., taking 110 g of the resol phenolic resin of step (1) and slowly stirring and dropping it into the modified rosin ester of step (2), continuing the reaction for 1 hour, removing the low boiling point fraction by vacuum distillation to obtain a silicon micropowder grafted rosin phenolic resin, adding it into palm oil with 1 / 5 times the volume of the silicon micropowder grafted rosin phenolic resin, rotating at 300 r / min, stirring for 30 minutes, and obtaining a modified rosin phenolic resin.

[0031] Preparation Example 4 The silica powder grafted rosin phenolic resin and polyketone resin prepared in Preparation Example 2 were mixed with the epoxy soybean oil modified acrylic resin prepared in Preparation Example 1 in a mass ratio of 2.5:1:1.5, added into palm oil of 1 / 5 times the volume of the above mixture, and stirred for 30 minutes at a speed of 300 r / min to obtain modified rosin phenolic resin.

[0032] Preparation Example 5 The silica powder grafted rosin phenolic resin and polyketone resin prepared in Preparation Example 3 and the epoxy soybean oil modified acrylic resin prepared in Preparation Example 1 were mixed in a mass ratio of 2.5:1:1.5, added into palm oil of 1 / 5 times the volume of the above mixture, and stirred for 30 minutes at a speed of 300 r / min to obtain modified rosin phenolic resin.

[0033] Preparation Example 6 The silica powder grafted rosin phenolic resin prepared in Preparation Example 2 and the epoxy soybean oil modified acrylic resin prepared in Preparation Example 1 were mixed in a mass ratio of 1:1, added into palm oil of 1 / 5 times the volume of the above mixture, and stirred at a speed of 300 r / min for 30 minutes to obtain modified rosin phenolic resin.

[0034] Preparation Example 7 The silicon powder grafted rosin phenolic resin and polyketone resin prepared in Preparation Example 2 in a mass ratio of 1:1 were added to 1 / 5 times the volume of palm oil, and stirred at a speed of 300 r / min for 30 minutes to obtain a modified rosin phenolic resin.

[0035] Preparation Example 8 (1) 0.7 g of octadecylamine and 73 g of solid formaldehyde with a concentration of 96% were added to 200 g of dodecylphenol, and the mixture was stirred and reacted at 110° C. for 2 h to obtain a resol phenolic resin; (2) 452 g of horsetail rosin was added to 48 g of pentaerythritol, and 1.2 g of zinc oxide was added, and an esterification reaction was carried out at 220° C. for 6 h to obtain rosin ester; Add 63 g of γ-methacryloxypropyltrimethoxysilane to 250 g of 45% ethanol solution, then add 150 g of silicon micropowder, heat at 100° C., stir and reflux for 3 h, filter and dry at 60° C. to obtain modified silicon micropowder; Under nitrogen protection, 57 g of rosin ester and 46 g of methyl acrylate were added, the temperature was maintained at 110°C, and 1.8 g of azobisisobutyronitrile was added dropwise. After the addition was completed, the reaction was continued for 3 h, and the low-boiling fraction was removed by vacuum distillation to obtain modified rosin ester; (3) Keeping the system temperature at 220° C., taking 110 g of the resol phenolic resin of step (1) and slowly stirring and dropping it into the modified rosin ester of step (2), continuing the reaction for 1 h, removing the low boiling point fraction by vacuum distillation to obtain rosin phenolic resin, adding 118 g of modified silica powder and stirring at 500 r / min for 10 min to obtain silica powder modified rosin phenolic resin, and then adding 1 / 5 times the volume of the silica powder modified rosin phenolic resin into palm oil, rotating at 300 r / min, stirring for 30 min to obtain modified rosin phenolic resin.

[0036] Preparation Example 9 0.7 g of octadecylamine and 73 g of solid formaldehyde with a concentration of 96% were added to 200 g of dodecylphenol, stirred, and reacted at 110°C for 2 h to obtain a resol phenolic resin; (2) 452 g of horsetail rosin was added to 48 g of pentaerythritol, 1.2 g of zinc oxide was added, and an esterification reaction was carried out at 220°C for 6 h to obtain rosin ester; Under nitrogen protection, 57g of rosin ester and 46g of methyl acrylate were added, the temperature was maintained at 100-120°C, and 1.8g of azobisisobutyronitrile was added dropwise. After the addition was completed, the reaction was continued for 3h, and the low-boiling fraction was removed by vacuum distillation to obtain modified rosin ester; (3) Keeping the system temperature at 220° C., taking 110 g of the resol phenolic resin of step (1) and slowly stirring and dropping it into the modified rosin ester of step (2), the reaction was continued for 1 hour, and the low boiling point fraction was removed by vacuum distillation to obtain rosin phenolic resin, which was added to palm oil with a volume of 1 / 5 times that of the rosin phenolic resin, and the mixture was stirred at a speed of 300 r / min for 30 minutes to obtain modified rosin phenolic resin.

[0037] Example 1 An offset frosted ink, comprising the following components in percentages: 80 g of the modified rosin phenolic resin prepared in Preparation Example 2, 5 g of frosted powder, 2 g of an adhesion promoter, 3 g of a superdispersant, 5 g of carbon black, and 5 g of an auxiliary agent, wherein the auxiliary agent is a leveling agent and a defoaming agent in a mass ratio of 1:1; The modified rosin phenolic resin, frosting powder, adhesion promoter, super dispersant and auxiliary agent prepared in Preparation Example 2 were stirred and mixed in proportion, and dispersed at a speed of 800 rpm for 15 minutes to obtain a pre-dispersion; then the pre-dispersion was ground on a three-roll mill at 30° C. for 30 minutes to obtain the offset frosting ink.

[0038] Example 2 An offset frosted ink, comprising the following components in percentages: 80 g of the modified rosin phenolic resin obtained in Preparation Example 3, 5 g of frosted powder, 2 g of an adhesion promoter, 3 g of a superdispersant, 5 g of carbon black, and 5 g of an auxiliary agent, wherein the auxiliary agent is a leveling agent and a defoaming agent in a mass ratio of 1:1; The modified rosin phenolic resin, frosting powder, adhesion promoter, super dispersant and auxiliary agent prepared in Preparation Example 3 were stirred and mixed in proportion, and dispersed at a speed of 800 rpm for 15 minutes to obtain a pre-dispersion; then the pre-dispersion was ground on a three-roll mill at 30° C. for 30 minutes to obtain the offset frosting ink.

[0039] Example 3 An offset frosted ink, comprising the following components in percentages: 80 g of the modified rosin phenolic resin prepared in Preparation Example 4, 5 g of frosted powder, 2 g of an adhesion promoter, 3 g of a superdispersant, 5 g of carbon black, and 5 g of an auxiliary agent, wherein the auxiliary agent is a leveling agent and a defoaming agent in a mass ratio of 1:1; The modified rosin phenolic resin, frosting powder, adhesion promoter, super dispersant and auxiliary agent prepared in Preparation Example 4 were stirred and mixed in proportion, and dispersed at a speed of 800 rpm for 15 minutes to obtain a pre-dispersion; then the pre-dispersion was ground on a three-roll mill at 30° C. for 30 minutes to obtain the offset frosting ink.

[0040] Example 4 An offset frosted ink, comprising the following components in percentages: 80 g of the modified rosin phenolic resin obtained in Preparation Example 5, 5 g of frosted powder, 2 g of an adhesion promoter, 3 g of a superdispersant, 5 g of carbon black, and 5 g of an auxiliary agent, wherein the auxiliary agent is a leveling agent and a defoaming agent in a mass ratio of 1:1; The modified rosin phenolic resin, frosting powder, adhesion promoter, super dispersant and auxiliary agent prepared in Preparation Example 5 were stirred and mixed in proportion, and dispersed at a speed of 800 rpm for 15 minutes to obtain a pre-dispersion; then the pre-dispersion was ground on a three-roll mill at 30° C. for 30 minutes to obtain the offset frosting ink.

[0041] Example 5 An offset frosted ink, comprising the following components in percentages: 80 g of the modified rosin phenolic resin obtained in Preparation Example 6, 5 g of frosted powder, 2 g of an adhesion promoter, 3 g of a superdispersant, 5 g of carbon black, and 5 g of an auxiliary agent, wherein the auxiliary agent is a leveling agent and a defoaming agent in a mass ratio of 1:1; The modified rosin phenolic resin, frosting powder, adhesion promoter, super dispersant and auxiliary agent prepared in Preparation Example 6 were stirred and mixed in proportion, and dispersed at a speed of 800 rpm for 15 minutes to obtain a pre-dispersion; then the pre-dispersion was ground on a three-roll mill at 30° C. for 30 minutes to obtain the offset frosting ink.

[0042] Example 6 An offset frosted ink, comprising the following components in percentages: 80 g of the modified rosin phenolic resin obtained in Preparation Example 7, 5 g of frosted powder, 2 g of an adhesion promoter, 3 g of a superdispersant, 5 g of carbon black, and 5 g of an auxiliary agent, wherein the auxiliary agent is a leveling agent and a defoaming agent in a mass ratio of 1:1; The modified rosin phenolic resin, frosting powder, adhesion promoter, super dispersant and auxiliary agent prepared in Preparation Example 7 were stirred and mixed in proportion, and dispersed at a speed of 800 rpm for 15 minutes to obtain a pre-dispersion; then the pre-dispersion was ground on a three-roll mill at 30° C. for 30 minutes to obtain the offset frosting ink.

[0043] Comparative Example 1 An offset frosted ink, comprising the following components in percentages: 80 g of the modified rosin phenolic resin obtained in Preparation Example 8, 5 g of frosted powder, 2 g of an adhesion promoter, 3 g of a superdispersant, 5 g of carbon black, and 5 g of an auxiliary agent, wherein the auxiliary agent is a leveling agent and a defoaming agent in a mass ratio of 1:1; The modified rosin phenolic resin, frosting powder, adhesion promoter, super dispersant and auxiliary agent prepared in Preparation Example 8 were stirred and mixed in proportion, and dispersed at a speed of 800 rpm for 15 minutes to obtain a pre-dispersion; then the pre-dispersion was ground on a three-roll mill at 30° C. for 30 minutes to obtain the offset frosting ink.

[0044] Comparative Example 2 An offset frosted ink, comprising the following components in percentages: 80 g of the modified rosin phenolic resin prepared in Preparation Example 9, 5 g of frosted powder, 2 g of an adhesion promoter, 3 g of a superdispersant, 5 g of carbon black, and 5 g of an auxiliary agent, wherein the auxiliary agent is a leveling agent and a defoaming agent in a mass ratio of 1:1; The modified rosin phenolic resin, frosting powder, adhesion promoter, super dispersant and auxiliary agent prepared in Preparation Example 9 were stirred and mixed in proportion, and dispersed at a speed of 800 rpm for 15 minutes to obtain a pre-dispersion; then the pre-dispersion was ground on a three-roll mill at 30° C. for 30 minutes to obtain the offset frosting ink.

[0045] Performance Testing The performance test of an offset frosted ink prepared in Examples 1-6 and Comparative Examples 1-2 was conducted using the following method: a. Adhesion test: refer to GB / T 17201979 Determination of paint film adhesion; b. Hardness test: refer to GB / T 6739-1996 Determination of paint film hardness by pencil method for paints and varnishes; c. Transfer rate test: weigh the standard coated paper m0 and record it, weigh the glass sheet m1, take 10ml of the tested ink and apply it on the glass sheet and weigh it as m2, the actual amount of ink is m2-m1; transfer the ink to the machine rubber roller, and then print it on the standard coated paper, weigh the coated paper as m3, m3-m0 is the amount of ink transferred to the coated paper, calculate the transfer percentage of the tested ink based on the amount of ink transferred to the coated paper and the actual amount of ink; d. Sand feeling: After the ink printing is cured, the frosting effect is evaluated visually and tactilely.

[0046] Performance see Table 1: Table 1 Performance test results Adhesion hardness Sandy Transfer rate Example 1 Level 2 3H Uniform, good concave and convex feeling 34.26％ Example 2 Level 2 2H Uniform, good concave and convex feeling 33.98％ Example 3 Level 1 4H Uniform, good concave and convex feeling 38.15％ Example 4 Level 1 3H Uniform, good concave and convex feeling 37.47％ Example 5 Level 1 3H Uniform, good concave and convex feeling 36.27％ Example 6 Level 1 4H Uniform, good concave and convex feeling 35.81％ Comparative Example 1 Level 2 2H Uneven, bumpy feeling 30.89％ Comparative Example 2 Level 2 H Uneven, poor convex and concave feeling 28.68％ As can be seen from Table 1, compared with Comparative Examples 1-2, the offset matte ink prepared in Examples 1-6 has better adhesion, hardness, sand feel, and transfer rate, indicating that the modified rosin phenolic resin of the present application is used as offset matte ink, which has the effect of enhancing the offset matte feel of the matte ink; forming a uniform matte surface with a strong three-dimensional sense, strong adhesion to the substrate, good transferability during printing, suitable for high-speed offset printing, and excellent printing adaptability.

[0047] Compared with Examples 1-2 and Examples 3-6, the applicant found that the use of a certain proportion of polyketone resin and epoxy soybean oil-modified acrylic resin on the basis of synthetic silicon powder grafted rosin phenolic resin is beneficial to the uniform transfer of frosted ink during offset printing; the modified rosin phenolic resin allows the frosted powder in the ink to be well dispersed, so that the frosted powder is transferred to the surface of the substrate through the printing press, which is uniform and has a good concave-convex feel, thereby enhancing the offset frosted feel of the frosted ink; the adhesion of the substrate is enhanced, and it is suitable for high-speed offset printing and has excellent printing adaptability.

[0048] The above are all preferred embodiments of the present application, and the protection scope of the present application is not limited thereto. Therefore, any equivalent changes made according to the structure, shape, and principle of the present application should be included in the protection scope of the present application.

Claims

1. A modified rosin phenolic resin, characterized in that: The invention comprises silicon micropowder grafted rosin phenolic resin, and the preparation method thereof comprises: preparing the silicon micropowder grafted rosin resin, and then modifying the silicon micropowder grafted rosin resin with phenolic resin.

2. The modified rosin phenolic resin according to claim 1, characterized in that: The preparation steps of the silicon powder grafted rosin phenolic resin include: (1) Add catalyst and formaldehyde to alkylphenol, stir, and react at 100-110°C for 2-5 hours to obtain resol phenolic resin; (2) Add rosin to polyol, add catalyst, carry out esterification reaction at 180-220°C for 6-9h to obtain rosin ester, add modified silica powder and methyl acrylate under nitrogen protection, keep the temperature at 100-120°C, then drop in initiator, continue reaction for 1-3h after dropwise addition, and distill under reduced pressure to obtain modified rosin ester; (3) Maintaining the system temperature at 200-220° C., slowly stirring and dropping the resol phenolic resin of step (1) into the modified rosin ester of step (2), continuing the reaction for 1-2 hours, and performing vacuum distillation to obtain a silicon micropowder-grafted rosin phenolic resin.

3. The modified rosin phenolic resin according to claim 2, characterized in that: The mass ratio of the rosin ester to the modified silicon micropowder is 1:(0.3-1.8).

4. The modified rosin phenolic resin according to claim 2, characterized in that: The modified silicon micropowder is silicon micropowder modified by a silane coupling agent containing unsaturated double bonds.

5. The modified rosin phenolic resin according to claim 1, characterized in that: The modified rosin phenolic resin also includes polyketone resin and epoxy soybean oil modified acrylic resin.

6. The modified rosin phenolic resin according to claim 5, characterized in that: The preparation method of the epoxy soybean oil modified acrylic resin comprises the following steps: taking hydroxyethyl acrylate and maleic anhydride as raw materials, mixing, adding triethylamine, stirring and reacting at 95-110° C. for 1-2 hours, adding phthalic anhydride and continuing the reaction for 1-1.5 hours, adding epoxy soybean oil, cooling the system to 60-75° C., adding hydroxyethyl methacrylate and diisocyanate, stirring and reacting for 3-5 hours, and obtaining the epoxy soybean oil modified acrylic resin.

7. The modified rosin phenolic resin according to claim 6, characterized in that: The molar ratio of the hydroxyethyl methacrylate to diisocyanate is (0.8-1.5):

1.

8. The method for preparing the modified rosin phenolic resin according to any one of claims 1 to 7, characterized in that: The following steps are involved: Add silicon powder grafted rosin phenolic resin, polyketone resin and epoxy soybean oil modified acrylic resin into palm oil, rotate at 200-300 r / min, stir for 20-30 min, and obtain modified rosin phenolic resin.

9. An offset frosted ink, characterized in that: The modified rosin phenolic resin comprises the modified rosin phenolic resin according to any one of claims 1 to 8, wherein the content of the modified rosin phenolic resin is 60-80wt%.

10. The offset frosted ink according to claim 9, characterized in that: The offset frosted ink further comprises the following components in percentages: 1-5wt% frosted powder, 1-3wt% adhesion promoter, 1-4wt% superdispersant, 0.8-5wt% carbon black, and the remainder being auxiliary agents.