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

Abstract

This application relates to the technical field of novel resins and their applications, specifically to a modified rosin phenolic resin, a preparation method thereof, and an offset matte ink. The modified rosin phenolic resin comprises a silica micropowder-grafted rosin phenolic resin. Its preparation method comprises preparing the silica micropowder-grafted rosin resin and then modifying the silica micropowder-grafted rosin resin with a phenolic resin. This resin is used in offset matte inks, enabling uniform and stable transfer of the matte ink to the surface of the substrate. It exhibits excellent transferability, a uniform matte finish, and a good embossing feel. It also effectively enhances substrate adhesion, making it suitable for high-speed offset printing and possessing excellent printability.

Description

Technical Field

[0001] The present application belongs to the technical field of novel resins and their applications, and specifically relates to a modified rosin phenolic resin, 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 tactile feel of matte ink.

[0003] Inks that have a matte feel, both visually and tactilely, place high demands on the printing material. However, current printing processes, especially in large-scale industrial production, inevitably present issues such as a poor sandy feel, white spots on the printed surface, ink loss, and poor adhesion, failing to meet the increasing demands of commercial printing. Therefore, there is an urgent need to develop a matte ink with a matte feel that exhibits excellent transfer properties, good transferability, a long on-press skinning life, and low heavy metal content. The primary film-forming resin for offset matte inks is rosin phenolic resin. However, when using rosin phenolic resins in matte inks, excessive addition of abrasive powder results in poor transferability and adhesion. Summary of the Invention

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

[0005] In a first aspect, the present application provides a modified rosin phenolic resin, which adopts the following technical solution:

[0006] A modified rosin phenolic resin comprises silicon micropowder grafted rosin phenolic resin. The preparation method comprises: preparing the silicon micropowder grafted rosin resin, and then modifying the phenolic resin with the silicon micropowder grafted rosin resin.

[0007] By modifying the unique honeycomb structure of rosin-phenolic resin, the offset ink film possesses excellent adhesion, fluidity, color development, and gloss. By grafting silica powder onto the rosin resin, the dispersion of the silica powder within the resin is increased, enhancing offset printing stability and improving the uniformity and stability of the ink. Small particles form on the offset ink surface, creating a matte effect. The silica powder is evenly dispersed within the ink layer, resulting in a good matte effect and reducing the amount of matte powder used. The ink has excellent transferability during printing, fast post-printing fixation, good transferability, and improved friction and light resistance. This results in a vibrant, bright, and evenly matte surface for printed products, a strong three-dimensional effect, and a good surface finish.

[0008] 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;

[0009] (2) Add rosin to polyol, add a catalyst, and carry out esterification reaction at 180-220°C for 6-9 hours to obtain rosin ester. Under nitrogen protection, add modified silica powder and methyl acrylate, maintain the temperature at 100-120°C, and then add initiator dropwise. After the addition is complete, continue the reaction for 1-3 hours, and distill under reduced pressure to obtain modified rosin ester;

[0010] (3) Maintaining the system temperature at 200-220° C., slowly stirring and adding the resol phenolic resin of step (1) to 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.

[0011] Preferably, the mass ratio of the rosin ester to the modified silica powder is 1:(0.3-1.8).

[0012] Preferably, the modified silicon micropowder is silicon micropowder modified by a silane coupling agent containing unsaturated double bonds.

[0013] By reacting formaldehyde with a catalyst in an alkylphenol solution to form a resol containing a large number of active hydroxymethyl groups, a condensate containing more phenolic structural units can be synthesized. By using a certain ratio of rosin ester to 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. This application inventively modifies the rosin ester with a silane coupling agent, allowing the modified rosin ester to react with the resol to obtain a silica powder-grafted rosin phenolic resin with a relatively stable structure and composition.

[0014] The modified rosin phenolic resin further comprises polyketone resin and epoxy soybean oil modified acrylic resin.

[0015] By adding polyketone resin and epoxy soybean oil modified acrylic resin to modified rosin phenolic resin and using them in combination with silica powder grafted rosin phenolic resin, the frosted ink is evenly transferred during offset printing, presenting a uniform and stable matte effect; silica powder grafted rosin phenolic resin enables silica powder to be well dispersed, allowing silica powder to be transferred to the surface of the substrate through the printing press; with the help of the unique honeycomb structure characteristics of silica powder grafted rosin phenolic resin, the wetting properties of solid substances such as silica powder are improved, making the frosted ink have good adhesion, fluidity, color development and frosted surface stability, and reducing the surface tension of offset printing; adding polyketone resin can improve the high temperature resistance, weather resistance and yellowing resistance of frosted ink on the one hand, and on the other hand, it can improve the frosted ink's resistance to high temperature, weather resistance and yellowing resistance. Phenolic resin has good compatibility and can jointly improve the wettability and dispersibility of silica powder in matte ink, making it have high gloss, high adhesion, high hardness and other characteristics. On this basis, epoxy soybean oil is added to modify acrylic resin. The 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. The toughness and viscosity of modified rosin phenolic resin are further improved by introducing epoxy. The offset ink prepared 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 material from decreasing, which is prone to local deinking, curling, poor transferability and transferability during the offset printing process, thereby affecting the quality and efficiency of offset printing.

[0016] 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 them, adding triethylamine, stirring and reacting them at 95-110° C. for 1-2 hours, then adding phthalic anhydride and continuing the reaction for 1-1.5 hours, then adding epoxy soybean oil, cooling the system to 60-75° C., adding hydroxyethyl methacrylate and diisocyanate, and stirring and reacting them for 3-5 hours to obtain the epoxy soybean oil-modified acrylic resin.

[0017] The molar ratio of the hydroxyethyl methacrylate to the diisocyanate is (0.8-1.5):1.

[0018] Any method for preparing epoxy soybean oil-modified acrylic resin can be used to prepare the modified acrylic resin of this application. This application selects the above-mentioned conventional modification process: a large number of hydroxyl groups are obtained by reacting hydroxyethyl acrylate and acid anhydride, which are 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 improving the adhesion of the system.

[0019] In a second aspect, the present application provides a method for preparing a modified rosin phenolic resin, which adopts the following technical scheme: a method for preparing a modified rosin phenolic resin, comprising the following steps: adding silicon micropowder grafted rosin phenolic resin, polyketone resin and epoxy soybean oil modified acrylic resin to palm oil, rotating at a speed of 200-300 r / min, stirring for 20-30 minutes, to obtain a modified rosin phenolic resin.

[0020] In a third aspect, the present application provides an offset frosted ink, which adopts the following technical solution:

[0021] An offset frosted ink comprises 60-80 wt% of modified rosin phenolic resin.

[0022] The offset frosted ink further comprises the following components in the following percentages: 1-5 wt% of frosted powder, 1-3 wt% of adhesion promoter, 1-4 wt% of hyperdispersant, 0.8-5 wt% of carbon black, and the balance being auxiliary agents.

[0023] By adopting the above technical solution, 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 conducive 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 relatively low. The frosting powder is transferred to the surface of the printing material through the printing press, further enhancing the offset frosting feeling of the frosting ink and the adhesion of the substrate. The frosting ink is suitable for high-speed offset printing and has excellent printing adaptability.

[0024] Preferably, the abrasive powder is polytetrafluoroethylene powder.

[0025] Preferably, the auxiliary agent is a leveling agent and a defoaming agent in a mass ratio of (1-3):1.

[0026] In summary, this application has the following beneficial effects:

[0027] 1. By grafting silica powder onto rosin resin, the dispersion performance of silica powder in the resin and the offset printing stability are increased, the uniformity and stability of the ink are 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 used, and having good transferability and fast fixing speed during printing. It can also improve the friction resistance and light resistance; make the printing effect of the printed matter bright and vivid, form a uniform matte surface, have a strong three-dimensional sense, and have a good surface effect.

[0028] 2. By adding polyketone resin, epoxy soybean oil-modified acrylic resin and silica powder-grafted rosin phenolic resin to the modified rosin phenolic resin, the matte ink is evenly transferred during offset printing, presenting a uniform and stable matte effect. The silica powder-grafted rosin phenolic resin enables good dispersion of the silica powder, and the prepared matte ink has good adhesion, fluidity, color development and frosted surface stability. The addition of polyketone resin improves the high temperature resistance, weather resistance and yellowing resistance of the matte ink. The addition of epoxy soybean oil-modified acrylic resin and vegetable oil modification improve the compatibility of acrylate and silica powder-grafted rosin phenolic resin, thereby enhancing the uniform dispersion of the modified rosin phenolic resin and further improving the toughness and viscosity of the modified rosin phenolic resin. The resulting offset printing ink has a fast fixing and drying speed, good transferability, high gloss, enhanced adhesion to the substrate, and is suitable for high-speed offset printing with excellent printing adaptability.

[0029] 3. Formaldehyde forms a resol phenolic resin containing a large amount of active hydroxymethyl groups in a solution of alkylphenol, which can be used to synthesize condensates of more phenol structural units. By using a certain ratio 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 uses a silane coupling agent to modify the rosin ester, 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

[0030] The present application is further described in detail below with reference to the embodiments.

[0031] raw material

[0032] 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; hyperdispersant is dispersant S-17000; leveling agent is; TEGO Glide B1484; defoaming agent is BYK-052; epoxidized soybean oil is purchased from Wuhan Jixin Yibang Biotechnology Co., Ltd.; acrylate is purchased from Hebei Kailian Biotechnology Co., Ltd., and the adhesion promoter is HU290; silicon micropowder product number: S299106; polytetrafluoroethylene micropowder brand SGW-140.

[0033] 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.

[0034] Preparation Example

[0035] Preparation example of epoxy soybean oil modified acrylic resin

[0036] Preparation Example 1

[0037] 52 g of hydroxyethyl acrylate and 27 g of maleic anhydride were mixed as raw materials, 0.4 g of triethylamine was added, and the mixture was stirred and reacted at 100 ° C for 1 hour. 22 g of phthalic anhydride was added and the reaction was continued for 1 hour. Then 55 g of epoxy soybean oil was added. After the system was cooled to 75 ° C, hydroxyethyl acrylate and isophorone diisocyanate were added, and the mixture was stirred and reacted for 3 hours to obtain epoxy soybean oil-modified acrylic resin, wherein the total amount of hydroxyethyl acrylate and isophorone diisocyanate was 10 g, and the molar ratio was 0.8:1.

[0038] Modified rosin phenolic resin

[0039] Preparation Example 2

[0040] 0.7 g of octadecylamine and 73 g of 96% solid formaldehyde were added to 200 g of dodecylphenol, stirred, and reacted at 110°C for 2 h to obtain a resol resin.

[0041] (2) 452 g of horsetail rosin was added to 48 g of pentaerythritol, and 1.2 g of zinc oxide was added, and the mixture was subjected to esterification reaction at 220° C. for 6 h to obtain rosin ester;

[0042] 63 g of γ-methacryloxypropyltrimethoxysilane was added to 250 g of 45% ethanol solution, and then 150 g of silicon micropowder was added. The mixture was heated at 100°C, stirred and refluxed for 3 h, filtered, and dried at 60°C to obtain modified silicon micropowder.

[0043] Under nitrogen protection, 57g of rosin ester, 17.1g of modified silica powder and 46g of methyl acrylate were added, the temperature was maintained 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 point fraction was removed by vacuum distillation to obtain modified rosin ester;

[0044] (3) Maintaining the system temperature at 220° C., 110 g of the resol phenolic resin of step (1) was slowly stirred and added dropwise to the modified rosin ester of step (2), and the reaction was continued for 1 hour. The low-boiling point fraction was removed by vacuum distillation to obtain a silicon micropowder-grafted rosin phenolic resin, which was added to palm oil with a volume of 1 / 5 times that of the silicon micropowder-grafted rosin phenolic resin, and the mixture was stirred at a speed of 300 r / min for 30 minutes to obtain a modified rosin phenolic resin.

[0045] Preparation Example 3

[0046] (1) 0.7 g of octadecylamine and 73 g of 96% solid formaldehyde were added to 200 g of dodecylphenol, stirred, and reacted at 110° C. for 2 h to obtain a resol resin;

[0047] (2) 452 g of horsetail rosin was added to 48 g of pentaerythritol, and 1.2 g of zinc oxide was added, and the mixture was subjected to esterification reaction at 220° C. for 6 h to obtain rosin ester;

[0048] 63 g of γ-methacryloxypropyltrimethoxysilane was added to 250 g of 45% ethanol solution, and then 150 g of silicon micropowder was added. The mixture was heated at 100°C, stirred and refluxed for 3 h, filtered, and dried at 60°C to obtain modified silicon micropowder.

[0049] Under nitrogen protection, 57g of rosin ester, 10.4g of modified silica powder and 46g of methyl acrylate were added, the temperature was maintained 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 point fraction was removed by vacuum distillation to obtain modified rosin ester;

[0050] (3) Maintaining the system temperature at 220° C., 110 g of the resol phenolic resin of step (1) was slowly stirred and added dropwise to the modified rosin ester of step (2), and the reaction was continued for 1 hour. The low-boiling point fraction was removed by vacuum distillation to obtain a silicon micropowder-grafted rosin phenolic resin, which was added to palm oil with a volume of 1 / 5 times that of the silicon micropowder-grafted rosin phenolic resin, and the mixture was stirred at a speed of 300 r / min for 30 minutes to obtain a modified rosin phenolic resin.

[0051] Preparation Example 4

[0052] 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, and added to palm oil (1 / 5 times the volume of the above mixture). The mixture was stirred at a speed of 300 r / min for 30 minutes to obtain a modified rosin phenolic resin.

[0053] Preparation Example 5

[0054] The silica powder-grafted rosin phenolic resin and polyketone resin prepared in Preparation Example 3 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, and added to palm oil (1 / 5 times the volume of the above mixture). The mixture was stirred at a speed of 300 r / min for 30 minutes to obtain a modified rosin phenolic resin.

[0055] Preparation Example 6

[0056] 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, and added to palm oil (1 / 5 times the volume of the above mixture). The mixture was stirred at a speed of 300 r / min for 30 minutes to obtain a modified rosin phenolic resin.

[0057] Preparation Example 7

[0058] The silica powder grafted rosin phenolic resin and polyketone resin prepared in Preparation Example 2 at a mass ratio of 1:1 were added to 1 / 5 of the above volume of palm oil at a speed of 300 r / min and stirred for 30 minutes to obtain modified rosin phenolic resin.

[0059] Preparation Example 8

[0060] (1) 0.7 g of octadecylamine and 73 g of 96% solid formaldehyde were added to 200 g of dodecylphenol, stirred, and reacted at 110° C. for 2 h to obtain a resol resin;

[0061] (2) 452 g of horsetail rosin was added to 48 g of pentaerythritol, and 1.2 g of zinc oxide was added, and the mixture was subjected to esterification reaction at 220° C. for 6 h to obtain rosin ester;

[0062] 63 g of γ-methacryloxypropyltrimethoxysilane was added to 250 g of 45% ethanol solution, and then 150 g of silicon micropowder was added. The mixture was heated at 100°C, stirred and refluxed for 3 h, filtered, and dried at 60°C to obtain modified silicon micropowder.

[0063] 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 point fraction was removed by vacuum distillation to obtain modified rosin ester;

[0064] (3) Maintaining the system temperature at 220° C., taking 110 g of the resol phenolic resin of step (1) and slowly stirring and adding it dropwise to the modified rosin ester of step (2), continuing the reaction for 1 hour, and removing the low-boiling point fraction by distillation under reduced pressure to obtain rosin phenolic resin, then adding 118 g of modified silica powder at 500 r / min and stirring for 10 minutes to obtain silica powder-modified rosin phenolic resin, and then adding 1 / 5 times the volume of the silica powder-modified rosin phenolic resin to palm oil, rotating at 300 r / min and stirring for 30 minutes to obtain modified rosin phenolic resin.

[0065] Preparation Example 9

[0066] 0.7 g of octadecylamine and 73 g of 96% solid formaldehyde 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;

[0067] 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 point fraction was removed by vacuum distillation to obtain modified rosin ester;

[0068] (3) Maintaining the system temperature at 220° C., 110 g of the resol phenolic resin obtained in step (1) was slowly stirred and added dropwise to the modified rosin ester obtained in step (2). The reaction was continued for 1 h. The low-boiling point fraction was removed by vacuum distillation to obtain the rosin phenolic resin. The resin was added to palm oil having a volume of 1 / 5 of the rosin phenolic resin, and stirred at a speed of 300 r / min for 30 min to obtain the modified rosin phenolic resin.

[0069] Example 1

[0070] An offset frosted ink, comprising the following components in the following 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 hyperdispersant, 5 g of carbon black, and 5 g of an additive, wherein the additive is a leveling agent and a defoaming agent in a mass ratio of 1:1;

[0071] 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; the pre-dispersion was then ground on a three-roll mill at 30° C. for 30 minutes to obtain the offset frosting ink.

[0072] Example 2

[0073] An offset frosted ink, comprising the following components in the following percentages: 80 g of the modified rosin phenolic resin prepared in Preparation Example 3, 5 g of frosted powder, 2 g of an adhesion promoter, 3 g of a hyperdispersant, 5 g of carbon black, and 5 g of an additive, wherein the additive is a leveling agent and a defoaming agent in a mass ratio of 1:1;

[0074] 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; the pre-dispersion was then ground on a three-roll mill at 30° C. for 30 minutes to obtain the offset frosting ink.

[0075] Example 3

[0076] An offset frosted ink, comprising the following components in the following 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 hyperdispersant, 5 g of carbon black, and 5 g of an additive, wherein the additive is a leveling agent and a defoaming agent in a mass ratio of 1:1;

[0077] 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; the pre-dispersion was then ground on a three-roll mill at 30° C. for 30 minutes to obtain the offset frosting ink.

[0078] Example 4

[0079] An offset frosted ink, comprising the following components in the following percentages: 80 g of the modified rosin phenolic resin prepared in Preparation Example 5, 5 g of frosted powder, 2 g of an adhesion promoter, 3 g of a hyperdispersant, 5 g of carbon black, and 5 g of an additive, wherein the additive is a leveling agent and a defoaming agent in a mass ratio of 1:1;

[0080] 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; the pre-dispersion was then ground on a three-roll mill at 30° C. for 30 minutes to obtain the offset frosting ink.

[0081] Example 5

[0082] An offset frosted ink, comprising the following components in the following percentages: 80 g of the modified rosin phenolic resin prepared in Preparation Example 6, 5 g of frosted powder, 2 g of an adhesion promoter, 3 g of a hyperdispersant, 5 g of carbon black, and 5 g of an additive, wherein the additive is a leveling agent and a defoaming agent in a mass ratio of 1:1;

[0083] 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; the pre-dispersion was then ground on a three-roll mill at 30° C. for 30 minutes to obtain the offset frosting ink.

[0084] Example 6

[0085] An offset frosted ink, comprising the following components in the following percentages: 80 g of the modified rosin phenolic resin prepared in Preparation Example 7, 5 g of frosted powder, 2 g of an adhesion promoter, 3 g of a hyperdispersant, 5 g of carbon black, and 5 g of an additive, wherein the additive is a leveling agent and a defoaming agent in a mass ratio of 1:1;

[0086] 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; the pre-dispersion was then ground on a three-roll mill at 30° C. for 30 minutes to obtain the offset frosting ink.

[0087] Comparative Example 1

[0088] An offset frosted ink, comprising the following components in the following percentages: 80 g of the modified rosin phenolic resin prepared in Preparation Example 8, 5 g of frosted powder, 2 g of an adhesion promoter, 3 g of a hyperdispersant, 5 g of carbon black, and 5 g of an additive, wherein the additive is a leveling agent and a defoaming agent in a mass ratio of 1:1;

[0089] 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; the pre-dispersion was then ground on a three-roll mill at 30° C. for 30 minutes to obtain the offset frosting ink.

[0090] Comparative Example 2

[0091] An offset frosted ink, comprising the following components in the following 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 hyperdispersant, 5 g of carbon black, and 5 g of an additive, wherein the additive is a leveling agent and a defoaming agent in a mass ratio of 1:1;

[0092] 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; the pre-dispersion was then ground on a three-roll mill at 30° C. for 30 minutes to obtain the offset frosting ink.

[0093] Performance testing

[0094] The performance test of the offset frosted ink prepared in Examples 1-6 and Comparative Examples 1-2 was conducted using the following method:

[0095] a. Adhesion test: refer to GB / T 1720-1979 Determination of paint film adhesion;

[0096] b. Hardness test: refer to GB / T 6739-1996 Paints and varnishes - Determination of film hardness by pencil method;

[0097] c. Transfer rate test: Weigh the standard coated paper (m0) and record it. Weigh the glass sheet (m1). Apply 10ml of the ink to the glass sheet and weigh it (m2). The actual amount of ink is m2-m1. Transfer the ink to the rubber roller and then print it on the standard coated paper. Weigh the coated paper (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.

[0098] d. Sand feeling: After the ink printing is cured, the frosted effect is evaluated visually and tactilely.

[0099] Performance is shown in Table 1:

[0100] Table 1 Performance test results

[0101] 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, concave and convex feeling 30.89％ Comparative Example 2 Level 2 H Uneven, poor concave and convex feel 28.68％

[0102] As can be seen from Table 1, compared with Comparative Examples 1-2, the offset frosted inks prepared in Examples 1-6 have better adhesion, hardness, sandy feel, and transfer rate, indicating that the modified rosin phenolic resin of the present application is used as an offset frosted ink, which has the effect of enhancing the offset frosted feel of the frosted ink; forming a uniform frosted surface with a strong three-dimensional effect, strong adhesion to the substrate, good transferability during printing, suitable for high-speed offset printing, and excellent printing adaptability.

[0103] 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 in combination with synthetic silica powder grafted onto rosin phenolic resin is beneficial to the uniform transfer of frosted ink during offset printing; the modified rosin phenolic resin also allows the frosted powder in the ink to be well dispersed, allowing the frosted powder to be transferred to the surface of the substrate through the printing press, with a uniform and good concave-convex feel, thereby enhancing the offset frosted feel of the frosted ink; the adhesion of the substrate is enhanced, making it suitable for high-speed offset printing and having excellent printing adaptability.

[0104] The above are all preferred embodiments of the present application, and are not intended to limit the scope of protection of the present application. Therefore, any equivalent changes made based on the structure, shape, and principle of the present application should be included in the scope of protection of the present application.

Claims

1. A modified rosin phenolic resin, characterized in that: The invention comprises a silicon micropowder grafted rosin phenolic resin, and its preparation method comprises: preparing a silicon micropowder grafted rosin resin, and then modifying the silicon micropowder grafted rosin resin with a phenolic resin; the preparation steps of the silicon micropowder grafted rosin phenolic resin comprise: (1) adding a catalyst and formaldehyde to an alkylphenol, stirring, and reacting at 100-110°C for 2-5h to obtain a resol phenolic resin; (2) taking rosin and adding it to a polyol, adding a catalyst, and carrying out an esterification reaction at 180-220°C for 6-9h to obtain a rosin ester, and nitrogen protection. Under protection, modified silica powder and methyl acrylate are added, the temperature is maintained at 100-120°C, and an initiator is added dropwise. After the addition is completed, the reaction is continued for 1-3 hours, and the modified rosin ester is obtained by vacuum distillation; (3) the system temperature is maintained at 200-220°C, the resol phenolic resin of step (1) is slowly stirred and added dropwise to the modified rosin ester of step (2), the reaction is continued for 1-2 hours, and vacuum distillation is performed to obtain silica powder grafted rosin phenolic resin; the modified silica powder is silica powder modified by a silane coupling agent containing unsaturated double bonds.

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

3. The modified rosin phenolic resin according to claim 1, wherein: The modified rosin phenolic resin further comprises polyketone resin and epoxy soybean oil modified acrylic resin.

4. The modified rosin phenolic resin according to claim 3, wherein: 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 them, adding triethylamine, stirring and reacting them at 95-110° C. for 1-2 hours, then adding phthalic anhydride and continuing the reaction for 1-1.5 hours, then adding epoxy soybean oil, cooling the system to 60-75° C., adding hydroxyethyl methacrylate and diisocyanate, and stirring and reacting them for 3-5 hours to obtain the epoxy soybean oil-modified acrylic resin.

5. The modified rosin phenolic resin according to claim 4, characterized in that: The molar ratio of the hydroxyethyl methacrylate to diisocyanate is (0.8-1.5):

1.

6. The method for preparing the modified rosin phenolic resin according to any one of claims 1 to 5, characterized in that: The following steps are involved: Add silica 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 minutes to obtain modified rosin phenolic resin.

7. An offset frosted ink, characterized by: The modified rosin phenolic resin comprises the modified rosin phenolic resin according to any one of claims 1 to 5, wherein the content of the modified rosin phenolic resin is 60-80 wt%.

8. The offset frosted ink according to claim 7, characterized in that: The offset frosted ink further comprises the following components in the following percentages: 1-5 wt % of frosted powder, 1-3 wt % of adhesion promoter, 1-4 wt % of hyperdispersant, 0.8-5 wt % of carbon black, and the balance being auxiliary agents.