Polyester-based decorative paper ink and preparation method thereof

Abstract

The invention relates to the technical field of paper ink, and discloses polyester-based decorative paper ink and a preparation method thereof.The preparation method comprises the following steps that S1, ramie fibers are pretreated; s3, in a nitrogen atmosphere, adding itaconic acid, phthalic anhydride and 1, 6-hexanediol into a reactor, stirring and mixing, continuously adding p-toluenesulfonic acid and hydroquinone, ending the reaction until no water is generated, then adding dibutyltin dilaurate, and carrying out reduced pressure reaction to obtain unsaturated polyester; s4, adding unsaturated polyester, the modified ramie fiber and hydrogen-containing silicone oil into a reactor, stirring and mixing, adding a platinum catalyst, and reacting to obtain a polyester-based intermediate; and S5, adding water-based acrylic resin, the polyester-based intermediate, a flatting agent and a dispersing agent into the reactor, and stirring to obtain the polyester-based decorative paper ink. The polyester-based decorative paper ink provided by the invention has good adhesive force, water resistance and wear resistance.

Description

Technical Field

[0001] This invention relates to the field of paper and ink technology, specifically to a polyester-based decorative paper and ink and its preparation method. Background Technology

[0002] With the rapid development of the decorative materials industry, decorative paper, as an important surface decoration material, is widely used in the surface decoration of products such as furniture, flooring, doors and windows, and cabinets. The performance and quality of decorative paper directly affect the appearance and service life of decorative products, and decorative paper ink, as a key material in the decorative paper printing process, has a significant impact on the printing effect and adhesion of the decorative paper. Currently, most decorative paper inks on the market use acrylic resin and polyurethane resin as film-forming substances. However, decorative paper inks made from these resins have problems such as poor adhesion when applied to polyester-based decorative paper. Therefore, developing a polyester-based decorative paper ink with excellent adhesion and good water resistance has become an urgent problem to be solved in the field of decorative paper printing materials. Summary of the Invention

[0003] (a) Technical problems to be solved

[0004] To address the shortcomings of existing technologies, this invention provides a polyester-based decorative paper ink and its preparation method, which exhibits good adhesion, water resistance, and abrasion resistance.

[0005] (II) Technical Solution

[0006] To achieve the above objectives, the present invention provides the following technical solution: a method for preparing polyester-based decorative paper ink, comprising the following steps:

[0007] S1. Add dried ramie fibers to an aqueous sodium hydroxide solution, react at room temperature, then wash with water until neutral, and dry for later use to obtain pretreated ramie fibers:

[0008] S2. The pretreated ramie fiber was mixed with 2-(trifluoromethyl)acrylic acid solution and sodium hypophosphite was added. After stirring at room temperature, the mixture was dried to remove water, then heated to carry out esterification reaction. After cooling to room temperature, the mixture was washed with water until neutral to obtain modified ramie fiber.

[0009] Grafting 2-(trifluoromethyl)acrylic acid onto pretreated ramie fibers introduces a large amount of fluorine. The shared electron pair of the carbon-fluorine bond (CF) is strongly biased towards the fluorine atom, giving the CF bond extremely high bond energy (far higher than the CH bond). Furthermore, the polarity of the CF bond causes the outer layer of the carbon chain to carry a dense negative charge. This structure leads to a significant reduction in the surface free energy of the paper ink, preventing water from spreading on the surface and resulting in good water resistance.

[0010] S3. Under a nitrogen atmosphere, itaconic acid, phthalic anhydride, and 1,6-hexanediol are added to a reactor and stirred. Then, p-toluenesulfonic acid and hydroquinone are added. The reaction is carried out at 140-150℃ for 2-4 hours until no more water is produced. Then, dibutyltin dilaurate is added, and the pressure is reduced to 0.06-0.08 MPa. The reaction is carried out at 120-130℃ for 4-5 hours to obtain unsaturated polyester.

[0011] S4. Add unsaturated polyester, modified ramie fiber, and hydrogen-containing silicone oil to a reactor, stir and mix, add platinum catalyst, and react at 100-110℃ for 20-30 min to obtain a polyester-based intermediate;

[0012] S5. Add water-based acrylic resin, polyester-based intermediate, leveling agent and dispersant to the reactor and stir for 30-35 minutes. After stirring, polyester-based decorative paper ink is obtained.

[0013] Further, in step S1, 1-1.2g of dried ramie fiber is added to 90-100mL of a sodium hydroxide aqueous solution with a mass fraction of 16-18%, reacted at room temperature, then washed with water until neutral, and dried at 55-58℃ for 10-11h to obtain pretreated ramie fiber.

[0014] Further, in step S2, 0.9-1g of pretreated ramie fiber is mixed with 80-100mL of 14-18mmol of 2-(trifluoromethyl)acrylic acid solution, and 0.2-0.3g of sodium hypophosphite is added. After stirring at room temperature, the mixture is dried at 50-55℃ for 20-23h to remove water, and then heated at 110-120℃ for esterification reaction for 80-90min. After cooling to room temperature, the mixture is washed with water until neutral to obtain modified ramie fiber.

[0015] Further, in S3, the ratio of itaconic acid, phthalic anhydride, 1,6-hexanediol, p-toluenesulfonic acid, hydroquinone, and dibutyltin dilaurate is 2.4-3.1 mmol: 2.4-3.1 mmol: 4.8-6.2 mmol: 0.03-0.04 g: 0.01 g: 0.02-0.04 g.

[0016] Furthermore, in S4, the ratio of unsaturated polyester, modified ramie fiber, hydrogen-containing silicone oil, and platinum catalyst is 1 mmol: 0.6-0.8 mmol: 5-6 mmol: 0.02-0.03 g.

[0017] Further, in step S5, 40-50 parts by weight of waterborne acrylic resin, 3-5 parts by weight of polyester-based intermediate, 0.2-0.3 parts by weight of leveling agent, and 0.1-0.2 parts by weight of dispersant are added to the reactor and stirred for 30-35 minutes. After stirring, polyester-based decorative paper ink is obtained.

[0018] Furthermore, in S5, the leveling agent is BYK-346 and the dispersant is OP-10.

[0019] Furthermore, it is prepared using the preparation method described in any one of claims 1 to 7.

[0020] (III) Beneficial Technical Effects

[0021] This invention involves the addition of alkenyl groups in unsaturated polyester and modified ramie fibers with hydrogen-containing silicone oil to form a cross-linked network. This network structure effectively prevents moisture penetration, allowing decorative paper ink to maintain good print pattern integrity and color stability even in humid environments or under conditions of prolonged water contact.

[0022] Water-based acrylic resin and polyester-based intermediates cross-link to form a three-dimensional network structure. The composite system of "rigid polyester skeleton + flexible fiber reinforcement + hydrophobic silicone oil protection" significantly improves the wear resistance of the ink layer. This makes the decorative paper ink less prone to blurring or peeling due to friction and scratches in high-friction applications such as furniture and flooring. Its wear resistance is superior to that of traditional decorative paper ink, while also improving its adhesion. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] To better understand the above technical solutions, the following will provide a detailed explanation of the technical solutions in conjunction with specific embodiments.

[0025] The solid content of the water-based acrylic resin is 50%.

[0026] Example 1

[0027] A method for preparing polyester-based decorative paper ink includes the following steps:

[0028] S1. Add 1g of dried ramie fiber to 90mL of a 16% sodium hydroxide aqueous solution, react at room temperature, then wash with water until neutral, and dry at 55℃ for 10h to obtain pretreated ramie fiber.

[0029] S2. Mix 0.9g of pretreated ramie fiber with 80mL of 14mmol 2-(trifluoromethyl)acrylic acid solution, add 0.2g of sodium hypophosphite, stir at room temperature, dry at 50℃ for 20h to remove water, then heat at 110℃ for esterification reaction for 80min, cool to room temperature and wash with water until neutral to obtain modified ramie fiber.

[0030] S3. Under a nitrogen atmosphere, 2.4 mmol of itaconic acid, 2.4 mmol of phthalic anhydride, and 4.8 mmol of 1,6-hexanediol were added to a reactor and stirred. Then, 0.03 g of p-toluenesulfonic acid and 0.01 g of hydroquinone were added. The reaction was carried out at 140 °C for 2 h until no more water was produced. Then, 0.02 g of dibutyltin dilaurate was added, the pressure was reduced to 0.06 MPa, and the reaction was carried out at 120 °C for 4 h to obtain an unsaturated polyester.

[0031] S4. Add 1 mmol of unsaturated polyester, 0.6 mmol of modified ramie fiber, and 5 mmol of hydrogen-containing silicone oil to a reactor, stir and mix, add 0.02 g of platinum catalyst, and react at 100 °C for 20 min to obtain a polyester-based intermediate.

[0032] S5. Add 40 parts by weight of waterborne acrylic resin, 3 parts by weight of polyester-based intermediate, 0.2 parts by weight of leveling agent BYK-346, and 0.1 parts by weight of dispersant OP-10 to the reactor and stir for 30 minutes. After stirring, polyester-based decorative paper ink is obtained.

[0033] Example 2

[0034] A method for preparing polyester-based decorative paper ink includes the following steps:

[0035] S1. Add 1.2g of dried ramie fiber to 100mL of 18% sodium hydroxide aqueous solution, react at room temperature, then wash with water until neutral, and dry at 58℃ for 11h to obtain pretreated ramie fiber.

[0036] S2. Mix 1g of pretreated ramie fiber with 100mL of 18mmol 2-(trifluoromethyl)acrylic acid solution, add 0.3g sodium hypophosphite, stir at room temperature, dry at 55℃ for 23h to remove water, then heat at 120℃ for esterification reaction for 90min, cool to room temperature and wash with water until neutral to obtain modified ramie fiber.

[0037] S3. Under a nitrogen atmosphere, 3.1 mmol itaconic acid, 3.1 mmol phthalic anhydride, and 6.2 mmol 1,6-hexanediol were added to a reactor and stirred. Then, 0.04 g p-toluenesulfonic acid and 0.01 g hydroquinone were added. The reaction was carried out at 150 °C for 4 h until no more water was produced. Then, 0.04 g dibutyltin dilaurate was added, the pressure was reduced to 0.08 MPa, and the reaction was carried out at 130 °C for 5 h to obtain an unsaturated polyester.

[0038] S4. Add 1 mmol of unsaturated polyester, 0.8 mmol of modified ramie fiber, and 6 mmol of hydrogen-containing silicone oil to a reactor, stir and mix, add 0.03 g of platinum catalyst, and react at 110 °C for 30 min to obtain a polyester-based intermediate.

[0039] S5. Add 50 parts by weight of waterborne acrylic resin, 5 parts by weight of polyester-based intermediate, 0.3 parts by weight of leveling agent BYK-346, and 0.2 parts by weight of dispersant OP-10 to the reactor and stir for 35 minutes. After stirring, polyester-based decorative paper ink is obtained.

[0040] Example 3

[0041] A method for preparing polyester-based decorative paper ink includes the following steps:

[0042] S1. Add 1.1g of dried ramie fiber to 98mL of a 17% sodium hydroxide aqueous solution, react at room temperature, then wash with water until neutral, and dry at 56℃ for 10h to obtain pretreated ramie fiber;

[0043] S2. Mix 0.96g of pretreated ramie fiber with 92mL of 15mmol 2-(trifluoromethyl)acrylic acid solution, add 0.2g of sodium hypophosphite, stir at room temperature, dry at 53℃ for 22h to remove water, then heat at 116℃ for 84min for esterification reaction, cool to room temperature and wash with water until neutral to obtain modified ramie fiber;

[0044] S3. Under a nitrogen atmosphere, 2.7 mmol itaconic acid, 2.7 mmol phthalic anhydride, and 5.4 mmol 1,6-hexanediol were added to a reactor and stirred. Then, 0.03 g p-toluenesulfonic acid and 0.01 g hydroquinone were added. The reaction was carried out at 140 °C for 3 h until no more water was produced. Then, 0.03 g dibutyltin dilaurate was added, the pressure was reduced to 0.06 MPa, and the reaction was carried out at 124 °C for 4 h to obtain an unsaturated polyester.

[0045] S4. Add 1 mmol of unsaturated polyester, 0.7 mmol of modified ramie fiber, and 5 mmol of hydrogen-containing silicone oil to a reactor, stir and mix, add 0.02 g of platinum catalyst, and react at 110 °C for 25 min to obtain a polyester-based intermediate.

[0046] S5. Add 46 parts by weight of waterborne acrylic resin, 4 parts by weight of polyester-based intermediate, 0.25 parts by weight of leveling agent BYK-346, and 0.1 parts by weight of dispersant OP-10 to the reactor and stir for 32 minutes. After stirring, polyester-based decorative paper ink is obtained.

[0047] Comparative Example 1

[0048] A method for preparing polyester-based decorative paper ink, referring to the preparation method of Example 3, except that acrylic acid is used instead of 2-(trifluoromethyl)acrylic acid (CAS 381-98-6), and other steps S3, S4, and S5 are the same.

[0049] S1. Add 1.1g of dried ramie fiber to 98mL of a 17% sodium hydroxide aqueous solution, react at room temperature, then wash with water until neutral, and dry at 56℃ for 10h to obtain pretreated ramie fiber;

[0050] S2. Mix 0.96g of pretreated ramie fiber with 92mL of 15mmol acrylic acid solution, add 0.2g of sodium hypophosphite, stir at room temperature, dry at 53℃ for 22h to remove water, then heat at 116℃ for esterification reaction for 84min, cool to room temperature and wash with water until neutral to obtain modified ramie fiber.

[0051] Comparative Example 2

[0052] A method for preparing polyester-based decorative paper ink, referring to the preparation method of Example 3, except that modified ramie fiber is not added.

[0053] S1. Under a nitrogen atmosphere, 2.7 mmol itaconic acid, 2.7 mmol phthalic anhydride, and 5.4 mmol 1,6-hexanediol were added to a reactor and stirred. Then, 0.03 g p-toluenesulfonic acid and 0.01 g hydroquinone were added. The reaction was carried out at 140 °C for 3 h until no more water was produced. Then, 0.03 g dibutyltin dilaurate was added, the pressure was reduced to 0.06 MPa, and the reaction was carried out at 124 °C for 4 h to obtain an unsaturated polyester.

[0054] S2. Add 1 mmol of unsaturated polyester and 5 mmol of hydrogen-containing silicone oil to the reactor, stir and mix, add 0.02 g of platinum catalyst, and react at 110 °C for 25 min to obtain a polyester-based intermediate;

[0055] S3. Add 46 parts by weight of waterborne acrylic resin, 4 parts by weight of polyester-based intermediate, 0.25 parts by weight of leveling agent BYK-346, and 0.1 parts by weight of dispersant OP-10 to the reactor and stir for 32 minutes. After stirring, polyester-based decorative paper ink is obtained.

[0056] Comparative Example 3

[0057] A method for preparing polyester-based decorative paper ink, referring to the preparation method of Example 3, except that itaconic acid is used instead of unsaturated polyester.

[0058] S1. Add 1.1g of dried ramie fiber to 98mL of a 17% sodium hydroxide aqueous solution, react at room temperature, then wash with water until neutral, and dry at 56℃ for 10h to obtain pretreated ramie fiber;

[0059] S2. Mix 0.96g of pretreated ramie fiber with 92mL of 15mmol 2-(trifluoromethyl)acrylic acid solution, add 0.2g of sodium hypophosphite, stir at room temperature, dry at 53℃ for 22h to remove water, then heat at 116℃ for 84min for esterification reaction, cool to room temperature and wash with water until neutral to obtain modified ramie fiber;

[0060] S3. Add 1 mmol itaconic acid, 0.7 mmol modified ramie fiber, and 5 mmol hydrogen-containing silicone oil to the reactor, stir and mix, add 0.02 g platinum catalyst, and react at 110 °C for 25 min to obtain the intermediate;

[0061] S4. Add 46 parts by weight of waterborne acrylic resin, 4 parts by weight of polyester-based intermediate, 0.25 parts by weight of leveling agent BYK-346, and 0.1 parts by weight of dispersant OP-10 to the reactor and stir for 32 minutes. After stirring, decorative paper ink is obtained.

[0062] Performance testing

[0063] Adhesion test: The decorative paper inks prepared in the examples and comparative examples were tested according to GB / T9286; Abrasion resistance test: The ink film surface was repeatedly rubbed with a damp cloth (containing a small amount of water) (force 500g) for 30 times, and then the color was observed to see if it faded; Water resistance test: The decorative paper inks prepared in the examples and comparative examples were tested according to GB / T1733 (room temperature test).

[0064] Table 1: Performance Tests

[0065]

[0066]

[0067] As shown in Table 1, the polyester-based decorative paper ink prepared by the present invention has good water resistance, abrasion resistance and adhesion.

[0068] Comparative Example 1 uses acrylic acid instead of 2-(trifluoromethyl)acrylic acid. The 2-(trifluoromethyl)acrylic acid molecule contains a trifluoromethyl group, and the shared electron pair of the carbon-fluorine bond (CF) is strongly biased towards the fluorine atom, giving the CF bond extremely high bond energy. Furthermore, the polarity of the CF bond gives the outer layer of the carbon chain a dense negative charge. This structure can significantly reduce the surface free energy of paper ink, preventing water from spreading on the surface and providing better water resistance. Acrylic acid does not have this special fluorine element structure and cannot give paper ink the same water resistance. Comparative Example 2 did not include modified ramie fiber. Modified ramie fiber was obtained by mixing pretreated ramie fiber with a 2-(trifluoromethyl)acrylic acid solution and then undergoing an esterification reaction. Ramie fiber itself possesses a certain strength and fiber structure. After modification, it not only introduces a water-resistant fluorine structure but also forms a synergistic effect with unsaturated polyester and hydrogen-containing silicone oil. In polyester-based decorative paper inks, modified ramie fiber can act as a reinforcing agent, working with other components to construct a cross-linked network and improve the overall performance of the ink layer. Performance: Comparative Example 2 showed an adhesion of 1, slight color fading, and a water resistance of 300. Compared to Examples 1-3, its adhesion, abrasion resistance, and water resistance were all inferior. This is because the lack of modified ramie fiber prevents the formation of an effective cross-linked network and reinforcing structure, leading to a decrease in the overall performance of the paper ink.

[0069] Comparative Example 3 used itaconic acid instead of unsaturated polyester. Unsaturated polyester can undergo an addition reaction with the alkenyl groups and hydrogen-containing silicone oil in modified ramie fibers to form a cross-linked network, effectively preventing water penetration. Simultaneously, it cross-links with water-based acrylic resin to form a three-dimensional network structure, improving the ink layer's abrasion resistance and adhesion. When used alone, itaconic acid cannot form this complex cross-linked structure or exert its corresponding synergistic effect. Performance: Comparative Example 3 had an adhesion of 1, slight color fading, and a water resistance of 316, which was inferior to Examples 1-3. This indicates that unsaturated polyester plays an irreplaceable role in improving the water resistance, abrasion resistance, and adhesion of polyester-based decorative paper inks. The use of itaconic acid instead of unsaturated polyester in Comparative Example 3 resulted in a decline in performance.

[0070] It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Unless otherwise specified, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0071] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

[0072] Those skilled in the art should understand that the above descriptions are merely several specific embodiments of the present invention, and not all embodiments.

Claims

1. A method for preparing polyester-based decorative paper ink, characterized in that, Includes the following steps: S1. Add dried ramie fibers to an aqueous sodium hydroxide solution, react at room temperature, then wash with water until neutral, and dry for later use to obtain pretreated ramie fibers: S2. The pretreated ramie fiber was mixed with 2-(trifluoromethyl)acrylic acid solution and sodium hypophosphite was added. After stirring at room temperature, the mixture was dried to remove water, then heated to carry out esterification reaction. After cooling to room temperature, the mixture was washed with water until neutral to obtain modified ramie fiber. S3. Under a nitrogen atmosphere, itaconic acid, phthalic anhydride, and 1,6-hexanediol are added to a reactor and stirred. Then, p-toluenesulfonic acid and hydroquinone are added. The reaction is carried out at 140-150℃ for 2-4 hours until no more water is produced. Then, dibutyltin dilaurate is added, and the pressure is reduced to 0.06-0.08 MPa. The reaction is carried out at 120-130℃ for 4-5 hours to obtain unsaturated polyester. S4. Add unsaturated polyester, modified ramie fiber, and hydrogen-containing silicone oil to a reactor, stir and mix, add platinum catalyst, and react at 100-110℃ for 20-30 min to obtain a polyester-based intermediate; S5. Add water-based acrylic resin, polyester-based intermediate, leveling agent and dispersant to the reactor and stir for 30-35 minutes. After stirring, polyester-based decorative paper ink is obtained.

2. The polyester-based decorative paper ink according to claim 1, characterized in that, In step S1, 1-1.2g of dried ramie fiber is added to 90-100mL of a sodium hydroxide aqueous solution with a mass fraction of 16-18%, reacted at room temperature, washed with water until neutral, and dried at 55-58℃ for 10-11h to obtain pretreated ramie fiber.

3. The polyester-based decorative paper ink according to claim 1, characterized in that, In step S2, 0.9-1g of pretreated ramie fiber is mixed with 80-100mL of 14-18mmol of 2-(trifluoromethyl)acrylic acid solution, and 0.2-0.3g of sodium hypophosphite is added. After stirring at room temperature, the mixture is dried at 50-55℃ for 20-23h to remove water. Then, it is heated to 110-120℃ for esterification reaction for 80-90min. After cooling to room temperature, it is washed with water until neutral to obtain modified ramie fiber.

4. The polyester-based decorative paper ink according to claim 1, characterized in that, In S3, the ratio of itaconic acid, phthalic anhydride, 1,6-hexanediol, p-toluenesulfonic acid, hydroquinone, and dibutyltin dilaurate is 2.4-3.1 mmol: 2.4-3.1 mmol: 4.8-6.2 mmol: 0.03-0.04 g: 0.01 g: 0.02-0.04 g.

5. The polyester-based decorative paper ink according to claim 1, characterized in that, In S4, the ratio of unsaturated polyester, modified ramie fiber, hydrogen-containing silicone oil, and platinum catalyst is 1 mmol: 0.6-0.8 mmol: 5-6 mmol: 0.02-0.03 g.

6. The polyester-based decorative paper ink according to claim 1, characterized in that, In step S5, 40-50 parts by weight of waterborne acrylic resin, 3-5 parts by weight of polyester-based intermediate, 0.2-0.3 parts by weight of leveling agent, and 0.1-0.2 parts by weight of dispersant are added to the reactor and stirred for 30-35 minutes. After stirring, polyester-based decorative paper ink is obtained.

7. The polyester-based decorative paper ink according to claim 1, characterized in that, In S5, the leveling agent is BYK-346 and the dispersant is OP-10.

8. A polyester-based decorative paper ink, characterized in that, It is prepared by the preparation method described in any one of claims 1 to 7.

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