An antibacterial printing ink containing sandalwood plant essential oil and a preparation method thereof

Abstract

The application relates to the technical field of inks, and discloses an antibacterial printing ink containing sandalwood plant essential oil and a preparation method thereof, which comprises 0-16 parts by weight of acrylic resin, 0-55 parts by weight of polyurethane resin, 0-5 parts by weight of alkyd resin, 0-85 parts by weight of color paste, 0-20 parts by weight of pigment and filler, 4-6.5 parts by weight of wax paste, 0-16 parts by weight of mineral oil and 4-12 parts by weight of betaine cyclodextrin-sandalwood essential oil microcapsules. The betaine cyclodextrin is used as the microcapsules, the sandalwood essential oil is wrapped and released slowly, the printing ink can continuously release the sandalwood fragrance, the sandalwood fragrance is pleasant and gentle, and the printing ink is suitable for fragrance printing, book printing, greeting card printing, calendar printing, cosmetic packaging and the like, visual and olfactory effects are organically combined, and the printed matter is more attractive. Meanwhile, the printing ink has unique antibacterial performance.

Description

Technical Field

[0001] This invention relates to the field of ink technology, specifically to an antibacterial printing ink containing sandalwood essential oil and its preparation method. Background Technology

[0002] Printing inks are mainly composed of binders, pigments, and fillers. Adding plant essential oils to printing inks can impart a fragrant aroma to the inks and printed materials, which has broad application prospects in high-end printing fields such as cosmetic packaging and holiday cards. Meanwhile, the development of high-performance inks, imbuing them with antibacterial, water-resistant, and high-temperature-resistant properties, has become a research hotspot in recent years.

[0003] Sandalwood essential oil is a plant essential oil extracted primarily from the heartwood of the sandalwood tree. It contains abundant active ingredients such as santalene and santalol. It possesses a pleasant and aromatic scent and has wide applications in aromatherapy, cosmetics, and high-end inks. β-Cyclodextrin has a unique cylindrical structure with an inner hydrophobic and outer hydrophilic component, exhibiting excellent inclusion properties for various small molecule compounds. It is widely used in the inclusion of plant essential oils and in drug sustained-release formulations. Improving the inclusion and sustained-release properties of β-cyclodextrin for plant essential oils and pharmaceutical compounds is of great significance. This invention aims to utilize betaine cyclodextrin-sandalwood essential oil microcapsules to impart a unique sandalwood aroma and antibacterial properties to inks. Summary of the Invention

[0004] The technical problem solved by this invention is to provide a printing ink with slow-release sandalwood essential oil and antibacterial properties.

[0005] The technical solution provided by this invention is: an antibacterial printing ink containing sandalwood essential oil, comprising 0-16 parts by weight of acrylic resin, 0-55 parts by weight of polyurethane resin, 0-5 parts by weight of alkyd resin, 0-85 parts by weight of color paste, 0-20 parts by weight of pigments and fillers, 1-2 parts by weight of anti-skinning agent, 3-3.5 parts by weight of drying agent, 4-6.5 parts by weight of wax paste, 0-16 parts by weight of mineral oil, 0-0.3 parts by weight of dispersant, and 4-12 parts by weight of betaine cyclodextrin-sandalwood essential oil microcapsules.

[0006] Furthermore, the color pastes include red color paste, transparent yellow color paste, and medium yellow color paste.

[0007] Furthermore, the pigments include iron white pigment, phthalocyanine blue powder, and spectral blue paste AG.

[0008] Furthermore, the preparation method of betaine cyclodextrin-sandalwood essential oil microcapsules is as follows: Quaternary ammonium salt modified cyclodextrin, sodium sulfonate modified cyclodextrin, and sandalwood essential oil in a mass ratio of 100:(78-86):(120-200) are added to distilled water, heated to 75-90℃, stirred and reacted for 4-8 hours, then the temperature is lowered to 50-70℃, stirred and encapsulated for 6-12 hours, filtered, the surface residual essential oil is washed with ethanol, and dried to obtain betaine cyclodextrin-sandalwood essential oil microcapsules.

[0009] Furthermore, the preparation method of quaternary ammonium salt modified cyclodextrin is as follows:

[0010] (1) Add β-cyclodextrin, 3-[(tert-butoxycarbonyl)amino]propionic acid, and N,N-dicyclohexylcarbodiimide in a mass ratio of 100:(35-70):(38-76) to N,N-dimethylformamide, react at 25-40℃ for 6-12h, add ethanol to precipitate, filter and wash with ethanol, add the product to dichloromethane, mix well and add trifluoroacetic acid, react at 20-35℃ for 3-6h, concentrate under reduced pressure, wash with sodium carbonate solution and ethanol in sequence, and dry to obtain amino-modified cyclodextrin.

[0011] (2) Add amino-modified cyclodextrin and 2-epoxypropyldodecyl dimethyl quaternary ammonium salt to N,N-dimethylformamide, react at 35-50℃ for 18-24h, add ethanol to precipitate, filter, wash with ethanol, and dry to obtain quaternary ammonium salt modified cyclodextrin.

[0012] Furthermore, (1) contains β-cyclodextrin, 3-[(tert-butoxycarbonyl)amino]propionic acid, and N,N-dicyclohexylcarbodiimide.

[0013] Furthermore, in (2), the mass ratio of amino-modified cyclodextrin to 2-epoxypropyldodecyl dimethyl quaternary ammonium salt is 100:(24-66).

[0014] Furthermore, the preparation method of sodium sulfonate modified cyclodextrin is as follows: add sulfonated cyclodextrin to distilled water, add sodium hydroxide, adjust the pH of the solution to 9-10, react at 30-45℃ for 30-60 min, filter, wash with distilled water, and dry to obtain sodium sulfonate modified cyclodextrin.

[0015] Furthermore, the preparation method of antibacterial printing ink containing sandalwood essential oil is characterized by mixing and shearing 0-16 parts by weight of acrylic resin, 0-55 parts by weight of polyurethane resin, 0-5 parts by weight of alkyd resin, 0-85 parts by weight of color paste, 0-20 parts by weight of pigments and fillers, and 0-0.3 parts by weight of dispersant, then adding 4-6.5 parts by weight of wax paste, 0-16 parts by weight of mineral oil, 1-2 parts by weight of anti-skinning agent, 3-3.5 parts by weight of drying agent, and 4-12 parts by weight of betaine cyclodextrin-sandalwood essential oil microcapsules, and mixing well to obtain antibacterial printing ink containing sandalwood essential oil.

[0016] The technical effects of this invention are:

[0017] This invention utilizes the esterification reaction of 3-[(tert-butoxycarbonyl)amino]propionic acid with the hydroxyl group of β-cyclodextrin, followed by the removal of the boc protecting group to obtain amino-modified cyclodextrin. The introduced amino group then reacts with the epoxy group of 2-epoxypropyldodecyldimethyl quaternary ammonium salt to obtain a novel quaternary ammonium salt-modified cyclodextrin.

[0018] This invention uses quaternary ammonium salt-modified cyclodextrin and sodium sulfonate-modified cyclodextrin as wall materials for microcapsules. During the encapsulation of sandalwood essential oil, the quaternary ammonium salt groups of the quaternary ammonium salt-modified cyclodextrin and the sodium sulfonate groups of the sodium sulfonate-modified cyclodextrin undergo electrostatic interactions and betaine-type reactions, resulting in cross-linking and forming a three-dimensional network structure. This creates a microcapsule wall material with a higher specific surface area, significantly improving the encapsulation amount and loading rate of sandalwood essential oil. The loading rate of sandalwood essential oil by the cyclodextrin-sandalwood essential oil reaches 26.3%-43.3%. This achieves a high encapsulation rate of sandalwood essential oil and good sustained-release performance.

[0019] This invention uses acrylic resin, polyurethane resin, alkyd resin, etc. as ink film-forming resins, and combines them with pigments, driers, wax pastes, mineral oils, betaine cyclodextrin-sandalwood essential oil microcapsules, etc., to obtain an antibacterial printing ink containing sandalwood essential oil. By using betaine cyclodextrin as microcapsules, the sandalwood essential oil is encapsulated and released slowly, allowing the ink to continuously release a sandalwood fragrance that is pleasant, mild, and long-lasting. It is suitable for scented printing, scriptures, greeting cards, calendars, cosmetic packaging, etc., organically combining visual and olfactory senses to make printed products more attractive.

[0020] The wall material of the cyclodextrin-sandalwood oil microcapsules of this invention is composed of quaternary ammonium salt-modified cyclodextrin and sodium sulfonate-modified cyclodextrin. During the encapsulation of sandalwood oil, the quaternary ammonium salt groups and sodium sulfonate groups undergo a betaine-type reaction, forming betaine groups with unique antibacterial activity and strong bactericidal effect, significantly improving the antibacterial performance of printing inks. Furthermore, the encapsulated sandalwood oil contains active sandalwoodene, sandalwood alcohol, and other components, which also have good antibacterial effects, further enhancing the antibacterial performance of printing inks. The inhibition zone diameter against Staphylococcus aureus reaches 13.2-23.5 cm, against Escherichia coli reaches 10.9-22.3 cm, and against Candida albicans reaches 7.2-18.4 cm. Detailed Implementation

[0021] The acrylic resin of this invention is designated JONCRYL 682. The polyurethane resin is designated MR-875. The alkyd resin is designated alkyd resin 307. The anti-skinning agent is designated ADDITOL XL 297. The drying agent is manganese isooctanoate. The wax paste is designated MINERPOL 221. The mineral oil is designated DF-1181. The dispersant is designated Dispex Ultra PX 4585. The sandalwood essential oil has CAS Registry Number 8006-87-9.

[0022] The preparation method of sulfonated cyclodextrin is as follows: In an ice-water bath, 5g of β-cyclodextrin is added to 15mL of concentrated sulfuric acid and reacted for 3h. Then, 27.5g of calcium carbonate is added, filtered, and 50mL of 95% ethanol aqueous solution is added. After standing for 12h, sodium carbonate is added to the filtrate to adjust the pH to 10.5. After filtration, the solution is concentrated, and 250mL of ethanol is added to precipitate the precipitate. The precipitate is filtered, washed, and dried to obtain sulfonated cyclodextrin. Example 1

[0023] (1) Add 5g of β-cyclodextrin, 1.75g ​​of 3-[(tert-butoxycarbonyl)amino]propionic acid, and 1.9g of N,N-dicyclohexylcarbodiimide to 60mL of N,N-dimethylformamide. React at 30℃ for 12h. Add ethanol to precipitate the product, filter, wash with ethanol, add the product to 40mL of dichloromethane, mix well, add 10mL of trifluoroacetic acid, react at 35℃ for 3h, concentrate under reduced pressure, wash with sodium carbonate solution and ethanol successively, and dry to obtain amino-modified cyclodextrin. The reaction mechanism is as follows:

[0024]

[0025] (2) Add 5g of amino-modified cyclodextrin and 1.2g of 2-epoxypropyldodecyl dimethyl quaternary ammonium salt to 80mL of N,N-dimethylformamide, react at 40℃ for 24h, add ethanol to precipitate, filter, wash with ethanol, and dry to obtain quaternary ammonium salt modified cyclodextrin.

[0026] (3) Add 3g of sulfonated cyclodextrin to 30mL of distilled water, add sodium hydroxide to adjust the pH of the solution to 9, react at 30℃ for 60min, filter, wash with distilled water, and dry to obtain sodium sulfonate modified cyclodextrin. The reaction mechanism is as follows:

[0027]

[0028] (4) Add 5g of quaternary ammonium salt modified cyclodextrin, 3.9g of sodium sulfonate modified cyclodextrin, and 6g of sandalwood essential oil to 150mL of distilled water, heat to 75℃, stir and react for 8h, then lower the temperature to 50℃, stir and embed for 6h, filter, wash the surface of residual essential oil with ethanol, dry, and obtain betaine cyclodextrin-sandalwood essential oil microcapsules. Weigh and calculate the loading rate.

[0029] (5) Mix 150g acrylic resin, 800g red pigment paste, and 5g iron white pigment and shear to disperse. Then add 40g wax paste, 10g anti-skinning agent, 35g drying agent, and 40g betaine cyclodextrin-sandalwood essential oil microcapsules and mix well to obtain antibacterial printing ink containing sandalwood essential oil. Example 2

[0030] (1) Add 5g of β-cyclodextrin, 2.2g of 3-[(tert-butoxycarbonyl)amino]propionic acid and 2.6g of N,N-dicyclohexylcarbodiimide to 80mL of N,N-dimethylformamide, react at 25℃ for 12h, add ethanol to precipitate, filter and wash with ethanol, add the product to 40mL of dichloromethane, mix well and add 15mL of trifluoroacetic acid, react at 20℃ for 6h, concentrate under reduced pressure, wash with sodium carbonate solution and ethanol in sequence, dry to obtain amino-modified cyclodextrin.

[0031] (2) Add 5g of amino-modified cyclodextrin and 2.2g of 2-epoxypropyldodecyl dimethyl quaternary ammonium salt to 100mL of N,N-dimethylformamide, react at 50℃ for 18h, add ethanol to precipitate, filter, wash with ethanol, and dry to obtain quaternary ammonium salt modified cyclodextrin.

[0032] (3) Add 3g of sulfonated cyclodextrin to 30mL of distilled water, add sodium hydroxide, adjust the pH of the solution to 10, react at 45℃ for 30min, filter, wash with distilled water, and dry to obtain sodium sulfonate modified cyclodextrin.

[0033] (4) Add 5g of quaternary ammonium salt modified cyclodextrin, 4.3g of sodium sulfonate modified cyclodextrin, and 7g of sandalwood essential oil to 250mL of distilled water, heat to 90℃, stir and react for 4h, then lower the temperature to 50℃, stir and embed for 12h, filter, wash the surface of residual essential oil with ethanol, dry, and obtain betaine cyclodextrin-sandalwood essential oil microcapsules. Weigh and calculate the loading rate.

[0034] (5) Mix 70g polyurethane resin, 20g alkyd resin, 500g transparent yellow paste and 250g medium yellow paste and shear and disperse them. Then add 40g wax paste, 5g mineral oil, 15g anti-skinning agent, 30g drying agent and 80g betaine cyclodextrin-sandalwood essential oil microcapsules, mix well and obtain antibacterial printing ink containing sandalwood plant essential oil. Example 3

[0035] (1) Add 5g of β-cyclodextrin, 3.1g of 3-[(tert-butoxycarbonyl)amino]propionic acid and 3.4g of N,N-dicyclohexylcarbodiimide to 100mL of N,N-dimethylformamide. React at 40℃ for 6h. Add ethanol to precipitate the product. After filtration, wash with ethanol. Add the product to 50mL of dichloromethane. Mix well and add 15mL of trifluoroacetic acid. React at 25℃ for 6h. Concentrate under reduced pressure. Wash with sodium carbonate solution and ethanol in sequence. Dry to obtain amino-modified cyclodextrin.

[0036] (2) Add 5g of amino-modified cyclodextrin and 3g of 2-epoxypropyldodecyl dimethyl quaternary ammonium salt to 100mL of N,N-dimethylformamide, react at 35℃ for 18h, add ethanol to precipitate, filter, wash with ethanol, and dry to obtain quaternary ammonium salt modified cyclodextrin.

[0037] (3) Add 3g of sulfonated cyclodextrin to 30mL of distilled water, add sodium hydroxide, adjust the pH of the solution to 10, react at 30℃ for 60min, filter, wash with distilled water, and dry to obtain sodium sulfonate modified cyclodextrin.

[0038] (4) Add 5g of quaternary ammonium salt modified cyclodextrin, 4.3g of sodium sulfonate modified cyclodextrin, and 8.5g of sandalwood essential oil to 200mL of distilled water, heat to 90℃, stir and react for 4h, then lower the temperature to 65℃, stir and embed for 10h, filter, wash the surface of residual essential oil with ethanol, dry, and obtain betaine cyclodextrin-sandalwood essential oil microcapsules. Weigh and calculate the loading rate.

[0039] (5) Mix 120g acrylic resin, 550g polyurethane resin, 25g alkyd resin, and 200g phthalocyanine blue pigment powder and shear to disperse. Then add 65g wax paste, 15g mineral oil, 18g anti-skinning agent, 32g drying agent, and 100g betaine cyclodextrin-sandalwood essential oil microcapsules and mix well to obtain antibacterial printing ink containing sandalwood essential oil. Example 4

[0040] (1) Add 5g of β-cyclodextrin, 3.5g of 3-[(tert-butoxycarbonyl)amino]propionic acid and 3.8g of N,N-dicyclohexylcarbodiimide to 100mL of N,N-dimethylformamide, react at 40℃ for 6h, add ethanol to precipitate, filter and wash with ethanol, add the product to 50mL of dichloromethane, mix well and add 20mL of trifluoroacetic acid, react at 20℃ for 6h, concentrate under reduced pressure, wash with sodium carbonate solution and ethanol in sequence, dry to obtain amino-modified cyclodextrin.

[0041] (2) Add 5g of amino-modified cyclodextrin and 3.3g of 2-epoxypropyldodecyl dimethyl quaternary ammonium salt to 100mL of N,N-dimethylformamide, react at 35℃ for 24h, add ethanol to precipitate, filter, wash with ethanol, and dry to obtain quaternary ammonium salt modified cyclodextrin.

[0042] (3) Add 3g of sulfonated cyclodextrin to 30mL of distilled water, add sodium hydroxide, adjust the pH of the solution to 10, react at 30℃ for 60min, filter, wash with distilled water, and dry to obtain sodium sulfonate modified cyclodextrin.

[0043] (4) Add 5g of quaternary ammonium salt modified cyclodextrin, 4.3g of sodium sulfonate modified cyclodextrin, and 10g of sandalwood essential oil to 250mL of distilled water, heat to 90℃, stir and react for 4h, then lower the temperature to 70℃, stir and embed for 10h, filter, wash the surface of residual essential oil with ethanol, dry, and obtain betaine cyclodextrin-sandalwood essential oil microcapsules. Weigh and calculate the loading rate.

[0044] (5) Mix 160g acrylic resin, 450g polyurethane resin, 50g alkyd resin, 60g pigment and filler photoluminescent blue paste AG, and 3g dispersant and shear disperse. Then add 60g wax paste, 160g mineral oil, 20g anti-skinning agent, 30g drying agent, and 120g betaine cyclodextrin-sandalwood essential oil microcapsules, mix well, and obtain antibacterial printing ink containing sandalwood plant essential oil.

[0045] The difference between Comparative Example 1 and Example 1 is that β-cyclodextrin was used instead of quaternary ammonium salt modified cyclodextrin.

[0046] (1) Add 5g of β-cyclodextrin, 3.9g of sodium sulfonate modified cyclodextrin, and 6g of sandalwood essential oil to 150mL of distilled water, heat to 75℃, stir and react for 8h, then lower the temperature to 50℃, stir and encapsulate for 6h, filter, wash the surface of residual essential oil with ethanol, dry, and obtain cyclodextrin-sandalwood essential oil microcapsules. Weigh and calculate the loading rate.

[0047] (2) Mix 150g acrylic resin, 800g red pigment paste, and 5g iron white pigment and shear to disperse. Then add 40g wax paste, 10g anti-skinning agent, 35g drying agent, and 40g cyclodextrin-sandalwood essential oil microcapsules and mix well to obtain printing ink containing sandalwood essential oil.

[0048] The difference between Comparative Example 2 and Example 1 is that β-cyclodextrin was used instead of sodium sulfonate modified cyclodextrin.

[0049] (1) Add 5g of quaternary ammonium salt modified cyclodextrin, 3.9g of β-cyclodextrin, and 6g of sandalwood essential oil to 150mL of distilled water, heat to 75℃, stir and react for 8h, then lower the temperature to 50℃, stir and embed for 6h, filter, wash the surface of residual essential oil with ethanol, dry, and obtain cyclodextrin-sandalwood essential oil microcapsules. Weigh and calculate the loading rate.

[0050] (2) Mix 150g acrylic resin, 800g red pigment paste, and 5g iron white pigment and shear to disperse. Then add 40g wax paste, 10g anti-skinning agent, 35g drying agent, and 40g cyclodextrin-sandalwood essential oil microcapsules and mix well to obtain printing ink containing sandalwood essential oil.

[0051] The difference between Comparative Example 3 and Example 1 is that β-cyclodextrin was used instead of sodium sulfonate modified cyclodextrin and quaternary ammonium salt modified cyclodextrin.

[0052] (1) Add 8.9g of β-cyclodextrin and 6g of sandalwood essential oil to 150mL of distilled water, heat to 75℃, stir for 8h, then lower the temperature to 50℃, stir for 6h for encapsulation, filter, wash the surface of residual essential oil with ethanol, dry, and obtain cyclodextrin-sandalwood essential oil microcapsules. Weigh and calculate the loading rate.

[0053] (2) Mix 150g acrylic resin, 800g red pigment paste, and 5g iron white pigment and shear to disperse. Then add 40g wax paste, 10g anti-skinning agent, 35g drying agent, and 40g cyclodextrin-sandalwood essential oil microcapsules and mix well to obtain printing ink containing sandalwood essential oil.

[0054] In betaine cyclodextrin-sandalwood oil microcapsules, the loading rate of sandalwood oil W = (M 总 -M 壁材 ) / M 壁材M 总 =Total mass of betaine cyclodextrin-sandalwood oil microcapsules. M 壁材 M represents the total mass of quaternary ammonium salt-modified cyclodextrin and sodium sulfonate-modified cyclodextrin. 总 -M 壁材 This refers to the quality of the sandalwood essential oil it contains.

[0055] Table 1. Sandalwood essential oil loading rate test

[0056]

[0057] The cyclodextrin-sandalwood oil microcapsules in Examples 1-4 achieved sandalwood oil loading rates of 26.3%-43.3%. This is because, during the inclusion process, the quaternary ammonium salt groups of the quaternary ammonium salt-modified cyclodextrin undergo electrostatic interactions and betaine-type reactions with the sodium sulfonate groups of the sodium sulfonate-modified cyclodextrin, resulting in cross-linking and the formation of a three-dimensional network structure. This creates a microcapsule wall material with a higher specific surface area, significantly improving the encapsulation amount and loading rate of sandalwood oil.

[0058] Comparative Example 1 uses β-cyclodextrin instead of quaternary ammonium salt modified cyclodextrin. β-cyclodextrin cannot undergo electrostatic interaction and betaine-type reaction with sodium sulfonate modified cyclodextrin. The two cannot form a three-dimensional spatial network structure. The specific surface area of ​​the microcapsule wall material is low, so the encapsulation amount and loading rate of sandalwood essential oil are low.

[0059] Comparative Example 2 uses β-cyclodextrin instead of sodium sulfonate-modified cyclodextrin, which cannot undergo electrostatic interaction and betaine-type reaction with quaternary ammonium salt-modified cyclodextrin. The two cannot form a three-dimensional spatial network structure, and the specific surface area of ​​the microcapsule wall material is low, resulting in a low coating amount and loading rate of sandalwood essential oil.

[0060] Comparative Example 3 showed that replacing sodium sulfonate-modified cyclodextrin and quaternary ammonium salt-modified cyclodextrin with β-cyclodextrin resulted in lower coating amount and loading rate of sandalwood essential oil.

[0061] Staphylococcus aureus, Escherichia coli, and Candida albicans were used as test strains. 0.5 mL of bacterial suspension (concentration of 106 CFU / mL) of the test strain was transferred and dropped onto the surface of a sterile petri dish. Then, 0.2 mL of printing ink was dropped onto the surface of sterilized filter paper. The filter paper was then placed in the petri dish and incubated at 37°C for 24 h in a constant temperature and humidity incubator. The diameter of the inhibition zone was then measured.

[0062] Table 2 Antibacterial Rate Test of Printing Inks

[0063]

[0064] The printing inks in Examples 1-4 exhibited inhibition zones of 13.2-23.5 cm in diameter against Staphylococcus aureus, 10.9-22.3 cm in diameter against Escherichia coli, and 7.2-18.4 cm in diameter against Candida albicans. This is because the wall material of the added cyclodextrin-sandalwood oil microcapsules is composed of quaternary ammonium salt-modified cyclodextrin and sodium sulfonate-modified cyclodextrin. During the encapsulation of sandalwood oil, the quaternary ammonium salt groups and sodium sulfonate groups undergo a betaine-type reaction, forming betaine groups with unique antibacterial activity and strong bactericidal effect, significantly improving the antibacterial performance of the printing ink. Furthermore, the encapsulated sandalwood oil contains active components such as santalene and santalol, which also have good antibacterial effects, further enhancing the antibacterial performance of the printing ink.

[0065] Comparative Example 1: β-cyclodextrin and sodium sulfonate modified cyclodextrin, used as microcapsule wall materials, do not contain betaine antibacterial groups. The printing ink has a low inhibition zone diameter against bacteria and poor antibacterial performance.

[0066] Comparative Example 2 uses β-cyclodextrin and quaternary ammonium salt modified cyclodextrin as microcapsule wall materials. The quaternary ammonium salt groups themselves also have strong antibacterial activity, which can significantly improve the antibacterial performance of printing ink. However, the microcapsule wall material has a low coating amount of sandalwood essential oil, resulting in a lower content of active antibacterial components such as sandalwoodene and sandalwood alcohol. Therefore, the diameter of the inhibition zone is lower than that of Example 1.

[0067] Comparative Example 3 used β-cyclodextrin as the microcapsule wall material. It did not contain antibacterial quaternary ammonium salts and betaine groups. The printing ink had a lower diameter of the inhibition zone against bacteria and poorer antibacterial performance.

Claims

1. An antibacterial printing ink containing sandalwood essential oil, characterized in that, The preparation method of the antibacterial printing ink containing sandalwood essential oil is as follows: (1) Add 5g of β-cyclodextrin, 1.75g ​​of 3-[(tert-butoxycarbonyl)amino]propionic acid and 1.9g of N,N-dicyclohexylcarbodiimide to 60mL of N,N-dimethylformamide, react at 30℃ for 12h, add ethanol to precipitate, filter and wash with ethanol, add the product to 40mL of dichloromethane, mix well and add 10mL of trifluoroacetic acid, react at 35℃ for 3h, concentrate under reduced pressure, wash with sodium carbonate solution and ethanol in sequence, dry to obtain amino-modified cyclodextrin; (2) Add 5g of amino-modified cyclodextrin and 1.2g of 2-epoxypropyldodecyl dimethyl quaternary ammonium salt to 80mL of N,N-dimethylformamide, react at 40℃ for 24h, add ethanol to precipitate, filter, wash with ethanol, and dry to obtain quaternary ammonium salt modified cyclodextrin. (3) Add 3g of sulfonated cyclodextrin to 30mL of distilled water, add sodium hydroxide, adjust the pH of the solution to 9, react at 30℃ for 60min, filter, wash with distilled water, and dry to obtain sodium sulfonate modified cyclodextrin. (4) Add 5g of quaternary ammonium salt modified cyclodextrin, 3.9g of sodium sulfonate modified cyclodextrin and 6g of sandalwood essential oil to 150mL of distilled water, heat to 75℃, stir and react for 8h, then lower the temperature to 50℃, stir and embed for 6h, filter, wash the surface of the essential oil with ethanol, dry, and obtain betaine cyclodextrin-sandalwood essential oil microcapsules; (5) Mix 150g acrylic resin, 800g red pigment paste, and 5g iron white pigment and shear to disperse. Then add 40g wax paste, 10g anti-skinning agent, 35g drying agent, and 40g betaine cyclodextrin-sandalwood essential oil microcapsules and mix well to obtain antibacterial printing ink containing sandalwood essential oil. The dextrin-sandalwood oil microcapsules had a sandalwood oil loading rate of 26.3%.

2. An antibacterial printing ink containing sandalwood essential oil, characterized in that, The preparation method of the antibacterial printing ink containing sandalwood essential oil is as follows: (1) Add 5g of β-cyclodextrin, 2.2g of 3-[(tert-butoxycarbonyl)amino]propionic acid and 2.6g of N,N-dicyclohexylcarbodiimide to 80mL of N,N-dimethylformamide, react at 25℃ for 12h, add ethanol to precipitate, filter and wash with ethanol, add the product to 40mL of dichloromethane, mix well and add 15mL of trifluoroacetic acid, react at 20℃ for 6h, concentrate under reduced pressure, wash with sodium carbonate solution and ethanol in sequence, dry to obtain amino-modified cyclodextrin; (2) Add 5g of amino-modified cyclodextrin and 2.2g of 2-epoxypropyldodecyl dimethyl quaternary ammonium salt to 100mL of N,N-dimethylformamide, react at 50℃ for 18h, add ethanol to precipitate, filter, wash with ethanol, and dry to obtain quaternary ammonium salt modified cyclodextrin. (3) Add 3g of sulfonated cyclodextrin to 30mL of distilled water, add sodium hydroxide, adjust the pH of the solution to 10, react at 45℃ for 30min, filter, wash with distilled water, and dry to obtain sodium sulfonate modified cyclodextrin. (4) Add 5g of quaternary ammonium salt modified cyclodextrin, 4.3g of sodium sulfonate modified cyclodextrin and 7g of sandalwood essential oil to 250mL of distilled water, heat to 90℃, stir and react for 4h, then lower the temperature to 50℃, stir and embed for 12h, filter, wash the surface of the essential oil with ethanol, dry, and obtain betaine cyclodextrin-sandalwood essential oil microcapsules; (5) Mix 70g polyurethane resin, 20g alkyd resin, 500g transparent yellow paste and 250g medium yellow paste and shear and disperse them. Then add 40g wax paste, 5g mineral oil, 15g anti-skinning agent, 30g drying agent and 80g betaine cyclodextrin-sandalwood essential oil microcapsules, mix well and obtain antibacterial printing ink containing sandalwood plant essential oil. The dextrin-sandalwood oil microcapsules had a sandalwood oil loading rate of 36.9%.

3. An antibacterial printing ink containing sandalwood essential oil, characterized in that, The preparation method of the antibacterial printing ink containing sandalwood essential oil is as follows: (1) Add 5g of β-cyclodextrin, 3.1g of 3-[(tert-butoxycarbonyl)amino]propionic acid and 3.4g of N,N-dicyclohexylcarbodiimide to 100mL of N,N-dimethylformamide, react at 40℃ for 6h, add ethanol to precipitate, filter and wash with ethanol, add the product to 50mL of dichloromethane, mix well and add 15mL of trifluoroacetic acid, react at 25℃ for 6h, concentrate under reduced pressure, wash with sodium carbonate solution and ethanol in sequence, dry to obtain amino-modified cyclodextrin; (2) Add 5g of amino-modified cyclodextrin and 3g of 2-epoxypropyldodecyl dimethyl quaternary ammonium salt to 100mL of N,N-dimethylformamide, react at 35℃ for 18h, add ethanol to precipitate, filter, wash with ethanol, and dry to obtain quaternary ammonium salt modified cyclodextrin. (3) Add 3g of sulfonated cyclodextrin to 30mL of distilled water, add sodium hydroxide, adjust the pH of the solution to 10, react at 30℃ for 60min, filter, wash with distilled water, and dry to obtain sodium sulfonate modified cyclodextrin. (4) Add 5g of quaternary ammonium salt modified cyclodextrin, 4.3g of sodium sulfonate modified cyclodextrin and 8.5g of sandalwood essential oil to 200mL of distilled water, heat to 90℃, stir and react for 4h, then lower the temperature to 65℃, stir and embed for 10h, filter, wash the surface of the essential oil with ethanol, dry, and obtain betaine cyclodextrin-sandalwood essential oil microcapsules; (5) Mix 120g acrylic resin, 550g polyurethane resin, 25g alkyd resin, and 200g phthalocyanine blue pigment powder and shear disperse them. Then add 65g wax paste, 15g mineral oil, 18g anti-skinning agent, 32g drying agent, and 100g betaine cyclodextrin-sandalwood essential oil microcapsules, mix well, and obtain antibacterial printing ink containing sandalwood plant essential oil. The dextrin-sandalwood oil microcapsules had a sandalwood oil loading rate of 43.3%.

4. An antibacterial printing ink containing sandalwood essential oil, characterized in that, The preparation method of the antibacterial printing ink containing sandalwood essential oil is as follows: (1) Add 5g of β-cyclodextrin, 3.5g of 3-[(tert-butoxycarbonyl)amino]propionic acid and 3.8g of N,N-dicyclohexylcarbodiimide to 100mL of N,N-dimethylformamide, react at 40℃ for 6h, add ethanol to precipitate, filter and wash with ethanol, add the product to 50mL of dichloromethane, mix well and add 20mL of trifluoroacetic acid, react at 20℃ for 6h, concentrate under reduced pressure, wash with sodium carbonate solution and ethanol in sequence, dry to obtain amino-modified cyclodextrin; (2) Add 5g of amino-modified cyclodextrin and 3.3g of 2-epoxypropyldodecyl dimethyl quaternary ammonium salt to 100mL of N,N-dimethylformamide, react at 35℃ for 24h, add ethanol to precipitate, filter, wash with ethanol, and dry to obtain quaternary ammonium salt modified cyclodextrin. (3) Add 3g of sulfonated cyclodextrin to 30mL of distilled water, add sodium hydroxide, adjust the pH of the solution to 10, react at 30℃ for 60min, filter, wash with distilled water, and dry to obtain sodium sulfonate modified cyclodextrin. (4) Add 5g of quaternary ammonium salt modified cyclodextrin, 4.3g of sodium sulfonate modified cyclodextrin and 10g of sandalwood essential oil to 250mL of distilled water, heat to 90℃, stir and react for 4h, then lower the temperature to 70℃, stir and embed for 10h, filter, wash the surface of the essential oil with ethanol, dry, and obtain betaine cyclodextrin-sandalwood essential oil microcapsules; (5) Mix 160g acrylic resin, 450g polyurethane resin, 50g alkyd resin, 60g pigment and filler photoluminescent blue paste AG, and 3g dispersant and shear disperse. Then add 60g wax paste, 160g mineral oil, 20g anti-skinning agent, 30g drying agent, and 120g betaine cyclodextrin-sandalwood essential oil microcapsules, mix well, and obtain antibacterial printing ink containing sandalwood plant essential oil. The dextrin-sandalwood oil microcapsules had a sandalwood oil loading rate of 37.5%.

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